A series of phosphorescent homo- and heterometallic copper(I)-chalcogenide clusters stabilized by cyclic (alkyl)(amino)carbene ligands [Cu4M4(mu(3)-E)(4)(CAAC(Cy))(4)] (M = Cu, Ag, Au; E = S, Se) has been synthesized by the reaction of the new copper(I) trimethylsilylchalcogenolate compounds [(CAAC(Cy))CuESiMe3] with ligand-supported group 11 acetates. The clusters are emissive E at 77 K in solution and the solid state, with emission colors that depend on the metal/chalcogen composition. Electronic structure calculations point to a common (3)[(M++E2-)LCT] emissive state for the series.