his mini-review summarizes the methods available for the synthesis of transition metal-sulfur complexes, which have been used as models of metalloprotein active sites, desulfurization catalysts, and organometallic functional materials. All the methods use silicon-sulfur compounds as starting materials, exploiting the selective cleavage of Si—S bond and the subsequent incorporation of sulfur fragment into the metal complex. Mechanistic considerations are also provided. Period covered: 1968 to date.