Four different well-defined cadmium monothiolate complexes of general formula (Tmp-Tol)CdSR (R = Bz, Ph, p-Tol, C6F5), where Tmp-Tol is the bulky tris(2-mercapto-1-p-tolylimidazolyl)borate ligand, have been readily synthesized in good yield. An X-ray structure of the phenylthiolate derivative confirmed the monomeric nature of the complexes and allowed the similarities in bond lengths and angles of the thione and thiolate donor groups to be verified at a single metal center.