The coordination behavior of [{CpMo(CO)(2)}(2)(mu,eta(2)-Sb-2)] (1; Cp = cyclopentadiene) toward Cu(I) was investigated. Its reaction with CuX (X = Br, Cl, and I) produced oligomers or polymers of the general formula [{CpMo(CO)(2)}(2)-(mu,eta(2)-Sb-2)(mu-CuX)](n). While 2 (X = Cl, n = 2) and 3 (X = Br, n = 2) proved to be halogen-bridged dimers in both solution and solid state, the molecules of 4 (X = 1, n = infinity) self-assembled in the crystal forming a linear polymer with a Cu-I skeleton supported by Sb-Cu bonds. The reaction of 1 with Cu[GaCl4] resulted in the formation of the ionic complex [{CpMo(CO)(2)}(2)(mu,eta(2)-Sb-2)](4)Cu-2[GaCl4](2) (5). Its dication contains four [{CpMo(CO)(2)}(2)(mu,eta(2)-Sb-2)] ligands arranged around a Cu-Cu dumbbell. All new compounds were characterized using IR, electrospray ionization mass spectrometry, H-1 NMR, elemental analysis, and single-crystal X-ray diffraction. The ligand was oxidized by both silver(I) and copper(II), and a cyclovoltammetric study revealed that 1 suffered irreversible reduction and oxidation in a dichloromethane solution at -2.04 and 0.10 V, respectively, versus ferrocene.