The poly(organo)phosphazenes (POPs) are inorganic-organic hybrid polymeric frameworks with a -P=N- skeleton and replaceable organic side groups. Due to their remarkable physical and chemical characteristics, the POPs have attracted significant attention for thermal stability and flame retardancy, chain flexibility, biocompatibility, radiation resistance, and biodegradability. Importantly, the POPs' PN backbone comprises high flexibility for substitution reactions to accommodate various functional organic moieties with a range of incorporated benzene-containing functional groups (-OH, -NH2, -SH, and others). These miscellaneous functional characteristics of POPs make them significant research candidates in diverse applications, including applications in sustainable membrane technologies for organic solvent nanofiltration (OSN) membranes, hydrogen/oxygen membrane barrier (H/OMB), ultrafiltration (UF), nanofiltration (NF), and gas separation (GS). The creation of novel membranes with adjustable characteristics and the ability to tolerate adverse mechanical, chemical, and thermal conditions is essential for the success of membrane-based processes in their commercialization. Recently, the POPs have made an important contribution to the preparation of highly stable membranes. In addition to outlining recent developments in their use in the fields of UF, NF, and GS, this review summarizes the primary synthesis pathways, properties, structure changes, and structure-property-relationships of POPs membranes. Finally, we discuss the prospects and challenges associated with the POPs in membrane technology.

Mitigating the polysulfide shuttling effect remains the most critical prerequisite for realizing lithium-sulfur (Li-S) batteries as viable next-generation energy storage systems, despite their remarkably high theoretical energy density. The concurrent challenges of lithium dendrite growth and uncontrolled polysulfide migration severely compromise rate capability, cycling stability, and areal capacity-particularly at higher sulfur loadings. To address these issues, we present a separator engineering strategy in which a polypropylene (PP) separator is modified with a phosphazene-based titanium MOF (Ti-MOF) and subsequently decorated with polyaniline, forming a PANI@Ti-MOF composite layer (denoted as PANI@TMMS). Benefiting from the electrical conductivity of polyaniline and the intrinsic catalytic activity of titanium centers, the PANI@TMMS coating exhibits a highly porous architecture, superior thermal stability, and robust electrochemical performance. Polysulfide adsorption studies confirm the strong binding affinity of this hybrid framework toward lithium polysulfides, ensuring their effective immobilization while maintaining uniform Li+ transport through interconnected nanochannels. The conductive polyaniline matrix further accelerates redox kinetics, promoting rapid polysulfide conversion and effectively suppressing the shuttle effect. As a result, the Li-S cells employing the PANI@TMMS separator deliver an impressive initial discharge capacity of 1330 mAh g- 1 at 0.1C, and maintain outstanding cycling stability with excellent capacity retention even under long-term operation at 1C. This scalable and versatile separator engineering strategy successfully integrates conductivity, catalytic functionality, and structural stability, advancing the development of high-performance Li-S batteries with superior efficiency, durability, and lifespan.

The inherent flammability of epoxy resins (EPs) limits their use in safety-critical fields. To improve their fire safety, a reactive phosphorus/nitrogen-containing flame retardant, denoted as CP-NH2, was prepared via the nucleophilic substitution of hexachlorocyclotriphosphazene. CP-NH2 is a compositional mixture of cyclophosphazene derivatives with different side-group types and substitution ratios. It contains amino and Schiff-base groups, which can participate in the curing and charring processes of EP. The incorporation of CP-NH2 markedly improved the flame retardancy of EP thermosets while maintaining good mechanical properties. At a phosphorus content of 0.31 wt %, the EP thermosets achieved a UL-94 V-0 rating and a limiting oxygen index of 30.2%. Compared with neat EP, the total heat release and total smoke production of EP-3CP decreased by 32% and 20%, respectively. Its tensile strength also increased by 13%. The flame-retardant mechanism was investigated by combining experimental thermal analysis with molecular simulations. The results indicate that CP-NH2 improves the flame retardancy of EP through a condensed-phase charring mechanism. The incorporation of CP-NH2 promotes the formation of a dense and continuous intumescent char layer during combustion. This protective layer acts as an effective barrier, retarding heat transfer, restricting oxygen diffusion, and suppressing the release of volatile degradation products. Overall, CP-NH2 provides an efficient route to improve the fire safety and mechanical performance of EP thermosets at a low phosphorus content. This work provides a facile and effective strategy for designing high-performance reactive intumescent flame retardants for fire-safe epoxy materials.

Stabilizing fluorinated emulsions with conventional surfactants remains a fundamental challenge. To address this, we designed and synthesized a novel class of amphiphilic, cyclophosphazene-based polymeric surfactants, leveraging the easily functionalizable core to introduce fluorinated alkyl chains and poly(ethylene glycol) (PEG) side groups. By precisely varying the ratio and length of these moieties, we tailored key properties, including hydrophilic-lipophilic balance (HLB), critical micelle concentration (CMC), and interfacial tension, to optimally stabilize fluorinated acrylate monomer emulsions. Subsequent polymerization of these oil-in-water (O/W) emulsions yielded well-defined fluoropolymer microspheres. Systematic investigation revealed that emulsion stability and final microsphere morphology are governed by surfactant architecture, concentration, cross-linker amount, water-to-oil ratio, and stirring speed. The resulting microspheres exhibited superhydrophobicity, with a static water contact angle of 152.8 degrees, highlighting their potential for self-cleaning coatings. This work not only validates cyclophosphazene-based surfactants as highly effective emulsifiers for fluorinated monomer polymerization but also provides a versatile platform for expanding the structural diversity and application scope of fluorinated polymers.

Biphasic liquid systems, serving as platforms with spatially directing functionality, achieve the integration of bio-mass nano-building blocks into advanced materials. Using liquid-liquid interfaces, a series of assemblies based on cellulose nanocrystals (CNCs) emerges, yet with limited application prospects, as the assemblies are mechanically fragile and thus incapable of withstanding processing-induced stresses. Here, we propose flexible cellulose nanofibrils (CNFs) as alternative assembling blocks and exploit their interfacial assembly to construct functional materials. Through an interfacial co-assembly strategy, CNFs spontaneously adsorb, assemble, and entangle at the water-toluene interface, forming reinforced yet elastic interfacial multi-layers. These assemblies are robust enough to yield multi-dimensional constructs, such as 3D porous foams and 1D biocompatible filaments, with recyclable oil-water separation and promising bioengineering applications.

The persistent challenges of multidrug resistance and systemic toxicity in cancer chemotherapy necessitate the development of intelligent, tumor-targeted co-delivery systems. Herein we report a novel nickel-based metal-organic framework (CUR + PTX@Ni-MOF) engineered with a phosphazene-derived ligand for the pH-responsive co-delivery of paclitaxel (PTX) and curcumin (CUR). The framework integrates a hexachlorocyclotriphosphazene (HCCP)-based linker featuring an intrinsically acid-labile P3N3 core enabling controlled degradation within the acidic tumor microenvironment (TME). The Ni-MOF exhibits a high BET surface area (177.118 m(2)/g) and a mesoporous architecture facilitating exceptional dual-drug loading capacities of 56.15% for CUR (96.3% encapsulation efficiency, EE) and 26.18% for PTX (43.01% EE). In vitro release studies demonstrated minimal drug leakage at physiological pH (7.4), while triggered, sustained release was achieved under acidic conditions (pH 6.5 and 5.0) with maximum cumulative releases of 75.42% for CUR and 49.35% for PTX at pH 5.0. Cellular assays confirmed high biocompatibility with normal LO2 hepatocytes (>80% viability) and potent, synergistic cytotoxicity against HeLa cancer cells driven by enhanced cellular uptake and apoptosis induction. This work establishes CUR + PTX@Ni-MOF as a promising, intrinsically pH-responsive platform for targeted and synergistic combination chemotherapy.

The self-assembly system driven by hydrogen bonding has been widely used in various fields. Two hydrogen-bonded cyclophosphazene derivatives with amino groups (AGHP) and carbonyl groups (CGHP) were synthesized by introducing hydrophobic groups and amino groups and hydrophilic groups and carbonyl groups into cyclophosphazene respectively through nucleophilic substitution. After they were dissolved in oil water two phases, stable emulsion, and self-loading membrane structures were obtained through self-loading behavior. The results indicate that strong hydrogen bonding can be formed between these two cyclic phosphazene derivatives with amino and carbonyl groups. This hydrogen bonding can significantly reduce the interfacial tension between water/oil phases (from around 33 mN/m to below 7 mN/m) and improve the interfacial coverage (which can reach over 80%). Meanwhile, under the hydrogen bonding between amino and carbonyl groups, an amphiphilic self-assembled film was obtained at the water oil interface. Through contact angle testing, it was found that the hydrophilic side of this self-assembled film had a contact angle of 77.5° and the hydrophobic side had a contact angle of 124.8°.

The successful treatment of cancer remains a significant challenge necessitating the development of advanced multifunctional platforms that combine diagnostics, targeting, and multiple therapeutic modalities. In this study, a novel, highly fluorescent, and magnetically guided nanocomposite HCCP-CUR-Ce6@M-MWNTs/N-CQDs-FA-PTX was engineered as an innovative approach to advanced multimodal cancer theranostics. The platform integrates N-doped carbon quantum dots (N-CQDs) functionalized with folic acid (FA) for precise tumor targeting and loading of the chemotherapeutic drug paclitaxel (PTX), yielding N-CQDs-FA-PTX. This targeted component is then combined with magnetic multiwalled carbon nanotubes (M-MWNTs) functionalized with hexachlorocyclotriphosphazene (HCCP), curcumin (CUR), and chlorin e6 (Ce6), which enable synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) effects. The fabricated nanoplatform exhibits high drug-loading efficiencies for both curcumin (CUR) and paclitaxel (PTX) with CUR integrated into the cross-linked HCCP framework and PTX effectively encapsulated by the nitrogen-doped CQDs functionalized with folic acid (N-CQDs-FA). This design enables synergistic chemo-photothermal and photodynamic therapy, efficiently inducing cancer cell ablation under 808 nm laser irradiation, and confirms pH-triggered rapid drug release at the targeted site. This multifunctional nanoplatform shows strong potential as an efficient and targeted strategy for comprehensive cancer treatment, representing a significant advancement in integrating imaging, chemotherapy (CT), and light-activated therapies into a single integrated system.

The development of high-performance epoxy resins (EP) with enhanced fire safety without compromising mechanical properties remains a critical challenge. Herein, a novel phosphazene-based iron metal-organic framework (Fe-MOF) was successfully synthesized via a hydrothermal method and employed as a multifunctional flame-retardant additive for epoxy composites. The incorporation of only 2 wt% Fe-MOF significantly improved fire resistance of EP, as evidenced by a 54.4% reduction in peak heat release rate (pHRR), along with substantial decreases in smoke production rate (SPR, 38.2%) and toxic CO/CO2 emissions (52.5% and 52.5%, respectively). These enhancements are attributed to the synergistic flame-retardant mechanism involving catalytic dense char formation from iron species, phosphorus-nitrogen synergism from the phosphazene ligand. Furthermore, the tensile strength of the composite also increased by 65%, indicating excellent matrix-filler compatibility. This work demonstrates that Fe-MOF is a highly efficient, ultralow-loading, and multifunctional flame retardant that simultaneously enhances fire safety and mechanical ductility of epoxy resins, offering a promising strategy for designing advanced polymer composites for high-safety applications.

Lithium-sulfur batteries (LSBs) are considered one of the most attractive next-generation energy storage technologies, offering a high theoretical energy density of 2600 Wh/kg along with environmental compatibility. However, the "shuttle effect" of lithium polysulfides (LiPSs) and low electrical conductivity severely hinder their practical application. Herein, we report a two-dimensional phosphazene-based covalent organic framework (HM-COF) modified commercial polypropylene (PP) separators (HM-COF/AB/PP). The HM-COF features abundant N/P elements and a porous structure, enabling electrostatic repulsion of LiPSs anions and efficient Li+ transport. The modified separator exhibits enhanced electrolyte wettability (contact angle reduced to 24°) and a Li+ transference number of 0.28 (vs 0.14 for pristine PP). XPS analysis confirms strong chemical adsorption of LiPSs by HM-COF. LSBs with HM-COF/AB/PP separators deliver an initial discharge capacity of 872 mAh/g at 0.5 C, with a low capacity decay rate of 0.059% per cycle, outperforming cells with pristine PP separators. This strategy provides a facile approach for fabricating high-performance LSBs.

The application of localized high-concentration electrolytes (LHCEs) has emerged as a promising approach to improve the performance of lithium metal batteries (LMBs). This study explores the use of a phosphazene-derived electrolyte as a nonflammable LHCE for high-voltage LMBs. Spectroscopic analyses, including Fourier transform infrared spectra (FTIR) and Raman spectroscopy, reveal the formation of the solvation structure in the electrolyte, which facilitates the development of stable solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI) layers. Compared to conventional ether-based electrolytes, the phosphazene-derived electrolyte significantly enhances interfacial stability, mitigating lithium dendrite formation, cathode decomposition and enabling prolonged cycling. Full-cell (Li| LiCoO2 (LCO)) tests demonstrate the cycling stability, achieving 67 % capacity retention after 100 cycles and good rate performance. X-ray photoelectron spectroscopy (XPS) results confirm that the interfaces formed with the phosphazene-derived electrolyte are enriched in LiF, Li3N, and Li3PO4, which contribute to improved interfacial strength and electrolyte compatibility. Galvanostatic cycling tests further highlight the dendrite suppression and stability of the electrolyte, with symmetrical cells (Li|Li) cycling for over 400 h at a current density of 2.5 mA/cm2. This work underscores the potential of phosphazenederived LHCEs to advance the development of high-energy-density and long-lasting LMBs.

Carbon nanotubes serve as highly effective fillers for enhancing the ablation performance of thermal insulation materials. However, their inherently high thermal conductivity often undermines the thermal insulation. In this study, cyclotriphosphazene-coated multi-walled carbon nanotubes (MWCNTs) were designed and successfully synthesized via an in-situ growth strategy. These coated MWCNTs were incorporated as fillers into poly(diaryloxyphosphazene) (PDAP) matrix to fabricate advanced thermal insulation materials. Compared to raw MWCNTs, the use of coated MWCNTs reduced the thermal conductivity of the PDAP composites by 18%. The ablation resistance was also improved, with linear ablation rate, mass ablation rate, and charring rate decreased by 34.6%, 27.1%, and 23.4%, respectively. Notably, a lowest charring rate of 0.07 mm/s has been achieved for elastomeric heat-shielding materials (EHSMs). The outstanding ablative performance is attributed to the carbonization-promoting effect of cyclotriphosphazenes and the formation of nano-network structures by MWCNTs. This structure enables simultaneous catalytic carbon formation, chemical vapor deposition, and graphitization reactions within the charred layer, resulting in a dense, high-strength, and intact charred layer. Cyclic ablation tests showed that the reinforced EHSMs retained their structural integrity and demonstrated reduced ablation rates even after repeated flame exposure. These findings suggest that cyclotriphosphazenecoated MWCNTs provide a promising pathway for developing high-performance EHSMs with superior thermal insulation and ablation resistance, meeting the demands of reusable aerospace systems and dual-pulse motors for next-generation aerospace exploration technologies.

The interfacial interaction between fibers and polyphosphazene is a crucial factor for efficient ablative resistance. Herein, a series of polyphosphazenes with aryloxy and substituted-aryloxy side groups were designed and synthesized, guided by molecular dynamics simulation. Effects of the type and position of the substitutions on properties of polyphosphazenes such as glass transition temperature (T g) were investigated. The introduction of polar chlorine-substituted side groups increases the interfacial interaction of polyphosphazenes with fibers, as evidenced by the binding energy and the number of hydrogen bonds, and the composites exhibited enhanced mechanical and ablative properties. The linear ablation, mass ablation, and charring rate of the composite reach 0.0148, 0.041, and 0.088 mm/s, respectively, which is superior to the composites using conventional rubbers as the matrix. These results make the chlorinated polyphosphazene a competitive candidate for thermal protection under the high-temperature service environment of vehicles and rockets.

Cyclotriphosphazenes (CTP) are regarded as an ideal class of inorganic-organic hybrid materials, known for their structural stability derived from their inorganic core (-P=N). CTP is an excellent precursor for the synthesis of co-doped carbon materials, suitable for various energy applications. Co-doped carbons offer micro/meso-porous structures, high specific surface area, good surface wettability, superior ion-transport and high capacitance, making them ideal for energy storage applications. Here, we report N, P and O ternary doped carbon nanosheets derived from cyclotriphosphazene-co-1,1-binaphthol (carbon precursor) by varying heating rate of 2, 5 and 10 degrees C min- 1 with enhanced char yield and 20 %-28 % oxygen content. The as synthesized carbon nanosheets are characterized using techniques like nuclear-magnetic resonance spectroscopy, X-ray diffraction, Raman and Xray photoelectron spectroscopy, Brunauer-Emmet-Teller analysis and scanning electron microscopy. The synthesized oxygen-enrich carbon nanosheets produced at 2 degrees C/min. exhibit a specific capacitance of 264F/g at a current density of 0.1 A/g in 1 M H2SO4 in a two-electrodes system. Notably, these carbon nanosheets demonstrates capacitance retention over 100 % after 10,000th cycles. At a power density of 24.68 W kg- 1 and a current density of 0.1 A/g, PBNS-2 delivers an energy density of 9.2 Wh kg-1, which decreased with increasing power density.

Epoxy resins (EPs) are widely used in high-tech industries due to their excellent mechanical, thermal, and electrical properties. However, their high dielectric constant, dielectric loss, and inherent flammability with heavy smoke release limit their application in advanced electronic packaging. To address these challenges, a multifunctional amino-fluorinated cyclophosphazene derivative (LCP-FNH2), incorporating amino groups, Schiff bases, and fluorinated side chains, was synthesized via nucleophilic substitutions of hexachlorocyclotriphosphazene (HCCP). The amino groups act as crosslinking agents, while the cyclophosphazene core and Schiff bases ensure flame retardancy and promote the formation of char layer. The fluorinated groups reduce dielectric constant and dielectric loss, and increase hydrophobicity of the resultant EP. Curing kinetics, thermal and mechanical properties, flame retardancy, and electrical properties were systematically investigated. The breakdown field strength increased by 17%, and volume resistivity improved by three orders of magnitude, compared with pristine EP. The dielectric constant and dielectric loss decreased by 22% and 14%, respectively. Moreover, the resultant EP maintained comparatively lower dielectric constant and dielectric loss at elevated temperatures. The fire safety was significantly improved with char yield increased by 66%, achieving V-0 rating in vertical combustion tests, and the total smoke production (TSP) decreased by 67%. Flame retardant mechanism from both condensed and gas phase aspects was comprehensively investigated and proposed. This work presents a feasible strategy for developing high-performance EP materials with integrated flame retardancy and superior dielectric properties for advanced electronic applications.

Carbon fiber-reinforced polymer composites are commonly used in ablative materials, but achieving a balance between thermal insulation, mechanical strength, and anti-ablation performance is challenging. This study presents a series of polyphosphazenes with trichloroethoxy substituents, which enhance the mechanical and thermal properties of the synthesized polyphosphazenes. The effects of different types and amounts of fiberized carbon fillers, including carbon fibers, carbon fiber powder, and carbon nanofibers, on the poly[(2,2,2-trichloroethoxy)/(aryloxy)] phosphazene composites were investigated. The composite reinforced with 10 phr (parts per hundred rubber) of fiberized carbon fillers showed a 49.1% reduction in linear ablation rate and 31.4% in charring ablation rate, compared with the baseline. The mechanical properties of the composite and charred layer improved by 57.5% and 215%, respectively. This is due to the fact that the carbon filler facilitates the formation of dense charred layers with low porosity and high graphitization, which prevent heat and flame penetration. The fiberized carbon-reinforced polyphosphazene composites exhibit excellent ablation resistance and mechanical performance, making them ideal for high-performance thermal insulation in extreme conditions.

Polyphosphazene-based materials offer a promising platform for targeted cancer drug delivery due to their excellent biocompatibility, biodegradability, and high drug-loading capacity. We developed a novel cyclomatrix polyphosphazene covalent organic framework (COF), HCCP-CUR COF for the co-delivery of hydrophobic anticancer drugs, via one-pot reaction of hexachlorocyclotriphosphazene (HCCP) and anti-cancer drug curcumin (CUR). For comparison, HCCP-HB-CUR COF was also fabricated using HCCP, CUR, and the pH-sensitive linker 4hydroxy-benzoic acid (4-hydroxy benzylidene)-hydrazide (HB). The hydrophobic anticancer drug paclitaxel (PTX) was then loaded into both COFs. PTX@HCCP-CUR demonstrated high loading capacities of 31.9 % for PTX and 64.25 % for CUR, with encapsulation efficiencies of 91.2 % and 70.15 %, respectively. PTX@HCCP-HB-CUR also showed efficient loading, with 25.1 % for PTX and 49.5 % for CUR, and encapsulation efficiencies of 77.5 % and 65.2 %, respectively. In vitro drug release studies at various pH confirmed the significant pH-responsive behavior of PTX@HCCP-CUR. PTX release dramatically increased from 31.7 % at a pH of 7.4 to 89.4 % under conditions of pH 4.0, CUR release showed a similar trend validating its inherent pH sensitivity without an explicit pH-responsive linker.While PTX@HCCP-HB-CUR exhibited enhanced release in acidic conditions PTX release increased to 94.6 % at pH 4.0, the substantial pH-responsive release observed in PTX@HCCP-CUR highlights its potential for tumor-targeted delivery. The present study demonstrates the significant potential of the PTX@HCCP-CUR COF system as a highly biocompatible and precisely pH-sensitive nanocarrier. This innovative system promises the co-delivery of hydrophobic anticancer drugs, specifically CUR and PTX, offering a path to optimize chemotherapeutic efficacy while simultaneously reducing systemic toxicity.

The non-metallic-Pt materials with high activities for oxygen reduction reaction (ORR) have attracted considerable attentions, but still face challenges related to the mismatched performance in device applications, especially for the atomic site catalysts. In this work, we propose a microenvironment-regulation strategy on introducing amino-fluorinated cyclotriphosphazene as grafting agents to address the critical issue on the mass-transfer limitations for the highly active and well-defined Fe─N 4 sites in phthalocyanine macrocycles. When this functional cyclotriphosphazene was grafted to polyphthalocyanines by the amidate linkage, the large steric hindrance of cyclotriphosphazene and the low surface energy of C─F bonding in fluorinate groups provide the enriched channels with low hygroscopicity, which guarantees the oxygen supply to Fe─N 4 sites and the hydroxyl leave from catalyst molecules. This microenvironment regulation improves the activities of catalyst molecules in electrochemical testing, and an amplified effect are also shown in the corresponding electrode assemblies. As results, the superior peak power densities of 178 mW cm −2 in aqueous Zn-air batteries (1.4-fold enhancements) and 616 mW cm −2 in alkaline membrane fuel cells (2.5-fold enhancements) are obtained. These findings offer a deeper understanding of non-Pt catalysts and provide a promising approach to their applications in advanced electrochemical devices.

Black phosphorus (BP) is a highly promising anode material for lithium‐ion batteries, boasting an exceptional theoretical capacity (2596 mAh g −1 ), a suitable lithiation potential (0.7 V vs Li + /Li), and favorable ion diffusion kinetics. However, its practical application is hampered by substantial volume expansion during cycling and the dissolution of soluble lithium polyphosphides (Li x Ps), leading to rapid capacity decay and poor cycling stability. To mitigate these issues, a novel 3D conductive polymer binder, denoted as “CP‐Si”; is developed. This binder is synthesized through in situ polymerization of poly( 3,4 ‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) using a silane‐functionalized carboxymethyl cellulose template. The CP‐Si network establishes robust cross‐linking via strong electrostatic and hydrogen‐bonding interactions, which significantly enhances the electrode's mechanical integrity and facilitates efficient electron transport. Furthermore, the abundant polar functional groups within CP‐Si effectively chemisorb Li x Ps intermediates, suppressing their shuttling and promoting the formation of a stable solid electrolyte interphase. As a result, the BP‐based anodes with the CP‐Si binder delivers outstanding long‐cycle performance, retaining a high reversible capacity of 741.0 mAh g −1 after 3000 cycles at a high current density of 2.0 A g −1 . This work provides a fundamental design strategy for multifunctional binders, paving the way for high‐performance, next‐generation energy storage devices.

High internal phase emulsion (HIPE) technology offers a robust approach to fabricating porous polymers with precise morphological control. However, monomers with high water solubility, such as methyl methacrylate (MMA) and hydroxyethyl methacrylate (HEMA), present significant challenges in forming stable water-in-oil HIPEs with the help of conventional surfactants. In this work, a series of amphiphilic polyphosphazenes (PPZs) with hydrophobic fluorine-containing segments and hydrophilic segments were synthesized via nucleophilic substitution reactions between poly(dichlorophosphazene) and various nucleophilic reagents. These PPZs were used to stabilize MMA and MMA-HEMA HIPEs by forming an anchoring layer at the water-oil interface. The resulting HIPEs demonstrated remarkable stability over 24 h with only 1 wt % PPZs. Porous PMMA and copolymers P(MMA-HEMA) with a controllable pore size were successfully synthesized via free radical polymerization. The porous PMMA exhibited excellent hydrophobic-oleophilic properties, achieving a maximum water contact angle of 159.8°. The porous PMMA also shows strong absorption performance to various organic solvents, with a maximum absorption capacity to dichloromethane of 3.9 g/g. Conversely, the porous P(MMA-HEMA) showed hydrophilicity with minimum water contact angles of 23° and a maximum absorption capacity to water of 1.9 g/g. Moreover, the effects of the molecular structures and the dosage of PPZs and the concentration of HEMA in the formulation on the morphologies and properties of the HIPEs and the corresponding porous polymers were comprehensively investigated. These notable performances endow the prepared porous PMMA and its copolymer P(MMA-HEMA) with exceptional potential for advanced applications in the field of adsorption. The developed material demonstrates efficacy in environmental remediation and resource recovery, particularly for capturing halogenated solvents (e.g., dichloromethane) and oxygenated residuals (e.g., ethyl acetate) in printing operations, regeneration of acetone-based semiconductor cleaning solutions, and emergency containment of marine hydrocarbon pollutants.