The reaction of [Cp2Mo2(CO)(4)(mu,eta(2:2)-E-2)] (A: E=P,B: E=As, Cp=C5H5) with the WCA-containing Cu(I)salts ([Cu(CH3CN)(4)][Al{OC(CF3)(3)}(4)] (CuTEF,C), [Cu(CH3CN)(4)][BF4] (D) and [Cu(CH3CN)(3.5)][FAl{OC6F10(C6F5)}(3)] (CuFAl,E)) affords seven unprecedented coordination compounds. Depending on the E(2)ligand complex, the counter anion of the copper salt and the stoichiometry, four dinuclear copper dimers and three trinuclear copper compounds are accessible. The latter complexes reveal first linear Cu(3)arrays linked by E(2)units (E=P, As) coordinated in an eta(2:1:1)coordination mode. All compounds were characterized by X-ray crystallography, NMR and IR spectroscopy, mass spectrometry and elemental analysis. To define the nature of the Cu...Cu...Cu interactions, DFT calculations were performed.