Main group metal, Bismuth, exists in different oxidation states (Bi + , Bi 2+ , Bi 3+ , Bi 5+ ) with Bi 3+ being the most stable ionic form, often observed in hybrid organic-inorganic compounds, doped inorganic lattices, and perovskites. The luminescent properties of Bi 3+ were extensively studied due to its broad luminescence feature in the visible and near-IR regions, while detailed spectroscopic studies are absent for bismuth-based coordination complexes. Recently, bismuth (Bi) based coordination complexes in oxidation state of +3 have attracted significant interest from the scientific community to explore their optoelectronic properties, as bismuth has a high spin orbit coupling (SOC) constant, is non-toxic among all its neighbors, and inexpensive. Additionally, the inherently richer structural diversity due to the stereochemically active 6s 2 lone pair of electrons can be controlled to harness multiple complexes with varied coordination numbers. The influence of lone pairs on the physicochemical properties makes Bi an intriguing material candidate for numerous applications like OLEDs, photocatalysis and solar cells. Such structural diversity lead bismuth to possess multiple structures with varied alignment of the electronic ground and excited state properties. Several bismuth containing small coordination complexes and coordination polymers were reported; however, the research was primarily limited to synthesis, structural description, and the supramolecular interactions in the complexes. The detailed mechanism of photophysical behavior considering the structure property relationship, the role of main ligand(s), ancillary ligand (chlorine, bromine and iodine ) and bismuth metal is still not well understood and hence require a systematic study to develop hybrid organic-inorganic systems able to challenge more widely used transition-metal complexes. (4) (Figure ). The detailed photophysical studies reveals the distinct contributions of the organic and inorganic parts in controlling and tuning the photophysical properties of the ground and excited state of the complexes. The experiments show that the ground state properties are strongly controlled by the inorganic part of the complexes while the emissive excited state is ligand based.