The production mechanism of Cu/Cl binary clusters were investigated by laser vaporization of CuCl, CuCl2, CuCl2·2H2O by time-of-flight mass spectrometry. We found that lager cluster size can be detected by using CuCl2·2H2O solid pellets than CuCl2 and CuCl. Only Cu+(CuCl)n, (CuCl)n, n <8 were observed when 532 um laser vaporized the CuCl. We also found almost the same cluster using CuCl2 and CuCl2·2H2O in the same mass range, deficit Cu clusters were dominated for clusters with more than five Cu atoms when using CuCl2, CuCl2·2H2O compounds. The relation of relative intensity In2:/In-1In+1 vs. different size of clusters were almost the same using different compounds above. (CuCl)3+.(CuCl)+6 ions in (CuCl)+n series, and Cu6Cl+5 in Cu(CuCl)+n series have special stability. The magic number observed above are different from those of alkali halide (MX) clusters, hexagonal structures were proposed for the above magic number clusters.