The first fused N-heterocyclic selone ligands, namely 2-(2′,6′-diisopropylphenyl)imidazole[1,5-a]pyridine-2-selone and 2-(2,4,6-trimethylphenyl) imidazole[1,5-a]pyridine-2-selone were isolated and their coordination ability was explored with bismuth trihalides to isolate the steric controlled bismuth(III) dinuclear complexes. Notably, a similar approach with N,N′-disubstituted imidazole selone, such as imidazole-1-methyl-3-(2-isopropyl)selone, gave the first polynuclear bismuth(III) selone chain. These new bismuth(III) selones were characterized by elemental analysis, FT-IR, multinuclear (1H and 13C) NMR spectroscopy, and single-crystal X-ray diffraction techniques. In solid-state structure, these new bismuth(III) selone complexes depict the unique coordination environment, geometry, and bonding features. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim