At room temperature, sufficiently grinding the mixtures of copper acetate with 1,2,4-triazole and benzotriazole separately resulted in the proceeding of the solid state reaction. It was found that the acetate acid flowed during the grinding. The heterocycle ligand 1,2,4-triazole or benzotriazole replaced the acetate and coordinates to Cu (II) to form a mixed ligands complex. The elementary analysis results show that the compositions of products were consistent with Cu (C2H2N3)(Ac).H2O and Cu (C6H4N3)(Ac).H2O, respectively. Infrared spectra of both complexes have exhibited the characteristics of C=N vibrations [Cu(C2H2N3)(Ac).H2O, 1,513 cm-1; Cu(C6H4N3)(Ac).H2O, 1,446 cm-1] for heterocycle ligands, C=O [Cu(C2H2N3)(Ac).H2O, 1,570 and 1,406 cm-1; Cu(C6H4N3)(Ac).H2O, 1,604 and 1,422 cm-1] for acetate and O-H (-3,400 cm-1) for water, respectively. The solid state reaction provides a way which is rapid, mild and in the absence of solvent for synthesized new complexes.