Copper(I) chloride complexes with various heterocyclic thiones and triphenylphosphine as ligands were prepared and characterized by elemental analysis, IR, UV-Vis and NMR spectroscopies. Crystal structures of the title compounds (complexes A and B, respectively) were determined by X-ray analysis. Crystals of complex A are yellow, monoclinic, space group P2(1)/c with a = 13.147(2), b = 18.592(3), c = 17.259(3) angstrom, beta = 97.45(2)-degrees, Z = 4. The final R value is 0.036 (R(W) = 0.036, gof = 1.8). Crystals of complex B are yellow, triclinic, space group P1BAR with a = 10.815(6), b = 13.109(2), c = 18.211(3) angstrom alpha = 110.87(1), beta = 100.55(4), gamma = 91.97(4)-degrees, Z = 2. The final R value is 0.060 (R(W) = 0.062, gof = 1.7). In both cases the asymmetric units include one complex molecule in which the bzimtH2 or nbzimtH2 act as monodentate ligands through the sulfur atom, as well as one solvent molecule (CH3COCH3) in the case of complex A. Inorganica Chimica Acta