The reaction of Ph 2 BiCl with (PhS)Li or (2,6-Me 2 C 6 H 3 S)Li yielded [Ph 2 BiSPh] ∞ (7) or Ph 2 BiS(2,6-Me 2 C 6 H 3 )] (8), respectively. Both compounds have been characterized by elemental analysis, melting point, FT-IR, FT-Raman, solution 1 H and 13 C{ 1 H} NMR, and X-ray crystallography. The solid-state structure of 7 is polymeric via long intermolecular Bi⋯S interactions and μ–SPh groups, yielding a distorted ψ-trigonal bipyramidal C 2 S 2 bonding environment for bismuth. Increasing steric bulk at the phenyl thiolate ligand in 8 results in the isolation of a monomeric species, which exhibits a distorted ψ-tetrahedral C 2 S bonding environment for bismuth. Comparison to previously reported structures of diorganobismuth chalcogenolates shows the effect of altering the chalcogen on intermolecular Bi⋯E (E=O, S, Se) bond formation. DFT calculations are employed to rationalize the bonding environments at bismuth and the observed polymeric structures. This work represents the first examples of structurally characterized R 2 BiSR′ species and advances our understanding of intermolecular bonding in bismuth chalcogenolates.