Copper(II) bisditolyl/dibenzyldithiophosphates [(RO)2PS2}2Cu] (R = o-, m- or p-CH3C6H4- or C6H5CH2-) were precipitated from aqueous solution of CuSO4.5H2O with sodium ditolyl/dibenzylphosphorodithioates, (RO)2PS2Na. These copper(II) complexes were reduced to copper(I) dithiophosphates by methanol corresponding to [{(RO)2PS2}Cu] in dichloromethane. The copper(I) complexes were then reacted with phosphorus and nitrogen donor ligands in methanol, which resulted in the formation of complexes [{(RO)2PS2}Cu].nL [n = 2, L = P(C6H5)3 and n = 1, L = C12H8N2] in 1:2 molar ratio. These compounds have been characterized by elemental analysis, molecular weight determination, magnetic moment, electronic, IR, and NMR (1H, 13C and 31P) spectroscopic measurements. Square planar geometry for the copper(II) complexes and tetrahedral geometry for the copper(I) complexes are suggested.