The synthesis and characterization of the copper and silver trimethylsilylchalcogenolates (EtPh2P)(3)MESiMe3 and (Et2PhP)(3)MESiMe3 (M = Cu-I, Ag-I) are reported. These chalcogenolate complexes can be prepared in high yield; however, they are thermally unstable. Low-temperature single-crystal X-ray analysis of (EtPh2P)(3)CuSSiMe3 (1b) and (Et2PhP)(3)CuSeSiMe3 (2a) confirms the terminal coordination of the chalcogen ligand and the tetrahedral coordination about the metal. Protonolysis of 2a with EtOH yields the terminal selenol complex (Et2PhP)(3)CuSeH (6). Reaction of 1b with EtPh2P-solubilized AgOAc yields the heterometallic cluster [Cu9Ag3S6(PEtPh2)(8)] (7) in good yield.