Reactions of CuCl with Te(Ph)SiMe3 and solublizing trialkylphosphine ligands afford a series of polynuclear copper-phenyltellurolate complexes that has been structurally characterized. The formation of the complexes is found to be highly dependent on the ancillary phosphine ligand used. The synthesis and structures of [Cu-2(mu -C TePh)(2)(PMe3)(4)] 1, [Cu-4(mu (3)-TePh)(4)(PPr3i)(3)] 2, [Cu-5(mu -TePh)(3)(mu (3)-TePh)(3)(PEt3)(3)][PEt3Ph] 3, and [Cu12Te3(mu (3)-TePh)(6)-(PEt3)(6)] 4 are described. The telluride (Te2-) ligands in 4 arise from the generation of TePh2 in the reaction mixtures. The subsequent co-condensation of clusters 3 and 4 leads to the generation of the nanometer sized complex [Cu29Te9(mu (3)-TePh)(10)(mu (4)-TePh)(2)(PEt3)(8)][PEt3Ph] 5 in good yield, in addition to small amounts of [Cu-39-(mu (3)-TePh)(10)(mu (4)-TePh)Te-16(PEt3)(13)] 6. These complexes are formed via the photo elimination of TePh2. The cyclic voltammogram of 5 in THF solution exhibits two oxidation waves, assigned to the oxidation of the Cu(I) centers.