We describe herein the synthesis and characterization of the first bis(mercaptoimidazolyl)borate complexes of bismuth, Bi(Bm^Me)₂X (X = Cl, Br, I). The chloro and bromo derivatives, whose molecular structures have been established by x-ray crystallography, display in the solid state distorted octahedral geometries in which one of the Bm^Me ligands is bidentate [SS] and the other exhibits a weak Bi^…H—B interaction and can be regarded as tridentate [SSH]. Reactivity studies of Bi(Bm^Me)₂Cl have provided several complexes having unusual [BiS₆] or [BiS₆H] cores, including dithiocarbamate, xanthate, and dithiophosphate derivatives. An overview of the preparation, spectroscopic and structural characterization, and thermal decomposition of these species will be described in this presentation.