Bismuth based coordination complexes are advantageous over other metal complexes, as Bismuth is the heaviest non-toxic element with high spin orbit coupling and potential optoelectronics applications. Herein, four Bismuth halide-based coordination complexes [Bi2Cl6(phen-thio)2] (1), [Bi2Br6(phen-thio)2] (2), [Bi2I6(phen-thio)2] (3), and [Bi2I6(phen-Me)2] (4) were synthesized, characterized and subjected to detailed photophysical studies. The complexes were characterized by single crystal X-ray diffraction, powder X-ray diffraction and NMR studies. Spectroscopic analysis of 1-4 in solutions of different polarities were performed to understand the role of organic and inorganic components in determining the ground and excited state properties of the complexes. The photophysical properties of the complexes were characterized by ground state absorption, steady state photoluminescence, microsecond time-resolved photoluminescence and absorption spectroscopy. Periodic Density Functional Theory (DFT) calculations were performed on the solid state structures to understand the role of organic and inorganic part of the complexes. The studies showed that changing the ancillary ligand from chlorine (Cl), bromine (Br) to iodine (I) bathochromically shifts the absorption band along with enhancing the absorption coefficient. Also, changing the halides (Cl, Br to I) affect the photoluminescent quantum yields of the ligand centered (LC) emissive state without markedly affecting the lifetimes. The combined results confirmed that ground state properties are strongly influenced by the inorganic part and the lower energy excited state is LC. This study paves the way to design novel bismuth coordination complexes for optoelectronic applications by rigorously choosing the ligands and bismuth salt.