The formation constants of the mixed-ligand complexes in the Cd(II), Cu(II) and Pb(II)-Trien-OH system were studied by polarograph. The formation constant $(log{eta}_{ij})$ was determined at $25^{circ}C$ in the ionic strength of 0.1. It was also confirmed that the mixed ligand complexes in this system were formed above pH 10.2, 10.5 and 9.0 for Cu(II), Cd(II) and Pb(II) by the calculation of the distribution for complexes at the various pH. Masking of Cd(II) by conversion to anionic EDTA-complexes has been used to separate Cu(II) from Cd(II) through passage of a combined Trien-EDTA solution on an cationic resin column. The optimal condition for the separation of Cu(II) from Cd(II) is confirmed at the pH range above 9.0, not only by considering the theoretical equation of the conditional-exchange-constant of metal on the cation exchange resin,but also by calculating the distribution of the mixed ligand complexes in the resin at the various pH with computer. By analyzing the synthetic sample of Cu(II) and Cd(II) with a EDTA masking at pH 9.5, it is found that the results of the experiment are satisfied with the theoretical value.