Abstract Schottky junctions are widely used to suppress charge recombination in photocatalysis, but their efficiency is often constrained by weak solar energy utilization, high interfacial resistance, and sluggish surface reaction kinetics. Plasmonic photocatalysis, driven by localized surface plasmon resonance (LSPR), offers a compelling route to simultaneously enhance light absorption, charge separation, and enable in situ photothermal heating. Here, we rationally design a plasmonic MoO2/ZnIn2S4 Schottky junction with well-defined interfacial Mo–S bonds and pronounced LSPR characteristics. These interfacial chemical bonds serve as efficient atomic-scale bridges to lower the interfacial barrier, thereby accelerating charge carrier transfer and separation. Meanwhile, the LSPR-induced photothermal effect significantly boosting surface reaction kinetics. The optimized 10-MO/ZIS achieves remarkable hydrogen evolution rates of 3.58 mmol·g–1·h–1 under visible light irradiation, corresponding to 11.9-fold enhancements over pristine ZnIn2S4. Notably, the apparent activation energy is substantially reduced from 42.4 to 25.9 kJ mol–1. Mechanistic studies reveal that the synergy between Mo–S bond-facilitated charge transport and LSPR-driven local heating is pivotal to the enhanced performance. This work establishes a new paradigm for integrating plasmonic effects with Schottky junctions to concurrently optimize charge dynamics and reaction kinetic for advanced solar fuel production.