The reactions of the phosphinoborane Ph2PBH2 center dot NMe3 with Cu-(I) halides [CuCl, CuBr, CuI] and [Cu(CH3CN)(4)BF4], respectively, were studied. Depending on the ratio of the reactants used, the former reaction allowed for the synthesis of eight neutral coordination compounds with the general formula [CunXn(Ph2PBH2 center dot NMe3)(m)] (X = Cl, Br, I; n = 1, 2, 4, 5; m = 2, 4) (4-11). The latter reaction, however, led to the formation of the homoleptic complex [Cu(Ph2PBH2 center dot NMe3)(3)][BF4] (13). The structures of the products 4-11 and 13 were compared to related complexes possessing the well-known Ph3P ligand. All compounds were characterized by single crystal X-ray structure analysis, multinuclear NMR spectroscopy, IR spectroscopy and mass spectrometry.