Copper(II) complexes with the 1: 1 condensation products of DL-phenylalanine and either 2- or 5-methyl-4-formylimidazole, [CuCl(HL2-Me)] (1) and [CuCl(HL5-Me)]center dot MeOH (2), were prepared, and their assembly structures were determined. Both complexes assumed two-dimensional (2D) assembly structures due to a helical chain structure constructed by the intermolecular imidazole-carboxyl ate hydrogen bond and interchain Cu*-Cl coordination bond. 2 crystallized in acentrosymmetric space group C222(1) showing a spontaneous resolution, while 1 crystallized in acentrosymmetric space group P2(1)/a.