In the present paper, the Raman peaks of complex in the CuCl2-H2O system and FeCl3-H2O system were studied in detail. In the CuCl2-H2O system, the superimposed characteristic peaks of various complex formed by Cu2+and Cl-(such as ［CuCl4］2- and ［CuCl6］4-) may be formed the peak of 286 cm-1, and the superimposed characteristic peaks of various complex formed by Cu2+ hydrate(［Cu(H2O)4］2+ and ［Cu(H2O)6］2+ based ) may be formed the peak of 412 cm-1 ; Through the analysis of peak parameters, we has founded two quantitative relationships : ① The peak intensity ratio (I1/I3 400 or I2/I3 400) of 286 cm-1(or 412 cm-1)and OH stretching Raman spectrum of water (at 3 400 cm-1) and concentration ; ② The integral area of 286 cm-1 (or 412 cm-1 ) and concentration. In the FeCl3-H2O system, 173 and 331 cm-1 might be attributed to ［FeCl4］- that is the most common form of FeCl3 complex in aqueous solution. The superimposed characteristic peaks of various complex formed by Fe3+and Cl-(such as ［FeCl］2+, ［FeCl2］+ etc) may be formed the broad peak of 173 cm-1, and the superimposed characteristic peaks of various complex formed by Fe3+ hydrate(［Fe(H2O)4］3+ and ［Fe(H2O)6］3+ based) may be formed the broad weak peak behind of 331 cm-1. Through the analysis of peak parameters, we has founded two quantitative relationships : ①The integral area of 331 cm-1(A2) and concentration ; ②The integral area ratio of 173 and 331 cm-1(A1/A2)and concentration.