The catalytic application of bismuth(iii) coordination polymers has been reported. Dinuclear bismuth(iii) chalcogenone complexes, namely, [(L1)2BiCl2(μ2-Cl)]2 (1), [(L2)2BiBr2(μ2-Br)]2 (4), a 2D layered bismuth(iii) thione complex [{(L2)BiCl2(μ2-Cl)}2]∞ (2), and 1D chain [(L1)Bi(Br)(μ2-Br)2·CH3CN]∞ (3), were isolated by treating the corresponding chalcogenone ligands [1-(2-hydroxyethyl)-3-isopropyl-1H-benzo[d]imidazole-2(3H)-selone (L1) and 1-(2-hydroxyethyl)-3-isopropyl-1H-benzo[d]imidazole-2(3H)-thione (L2)] with BiX3 (X = Cl, Br). Complexes 1-4 were characterized by FTIR and NMR spectroscopy, CHNS analysis, and single-crystal X-ray diffraction techniques. Besides, complexes 1-4 were utilized as catalysts in C-S cross-coupling reactions. Catalysts 1-4 were highly active. Interestingly, the 1D coordination polymer 3 displayed superior catalytic efficiency to discrete complexes 1 and 4 and the thione-based 2D coordination layer 2. The scope of the catalytic reaction was demonstrated using catalyst 3 for annulated heterocyclic aryl halides such as 9-chloro acridine and gave excellent yields. © 2022 The Royal Society of Chemistry