The redox-active diphosphine ligand 1,1'-bis(diphenylphosphino)ferrocene (dppf) has been used to stabilize the copper(1) chalcogenide clusters [Cu-12(mu(4)-S)(6)(mu-dppf)(4)] (1), [Cu-8(mu(4)-Se)(4)(mu-dppf)(3)] (2), [Cu-4(mu(4)-Te) (mu(4)-eta(2)-Te-2)(mu-dppf)(2)] (3), and [Cu-12(mu(5)-Te)(4)(mu(8)-eta(2)-Te-2)(2)(mu-dppf)(4)] (4), prepared by the reaction of the copper(I) acetate coordination complex (dppf)CuOAc (5) with 0.5 equiv of E(SiMe3)(2) (E = S, Se, Te). Single-crystal X-ray analyses of complexes 1-4 confirm the presence of {Cu2xEx} cores stabilized by dppf ligands on their surfaces, where the bidentate ligands adopt bridging coordination modes. The redox chemistry of cluster 1 was examined using cyclic voltammetry and compared to the electrochemistry of the free ligand dppf and the corresponding copper(I) acetate coordination complex 5. Cluster 1 shows the expected consecutive oxidations of the ferrocene moieties, Cu-I centers, and phosphine of the dppf ligand.