Cobalt(II) tri-tert-butoxysilanethiolates with 2,5-dimethylpyridine, 3,4-dimethylpyridine and 3,5-dimethylpyridine co-ligands have been synthesized by reaction ofwith the appropriate pyridines. The complexes were characterized by elemental analysis, single-crystal X-ray structure determination, IR and UV-Vis spectroscopy. These complexes are tetraor penta-coordinated with CoN 2 S 2 and CoNO 2 S 2 cores, respectively.