In this work, the effects of the concentrations of Cu (II), Zn (II) and Sn (II) ions in electrolytic bath solution on the properties of electrochemically deposited CuZnSn (CZT) films were investigated. The study of the composition of the CZT film has shown that the metallic content (relative atomic ratio) in the film increased linearly with the increase of the metal ion concentration. It is the first time that the relationship of the compositions of the alloy phases in the co-electrodeposited CZT film with the concentration of metal ions was revealed. The results have confirmed that the formantion and content of Cu6Sn5 and Cu5Zn8 alloy phases in the film were directly controlled by the concentration of Cu (II). SEM measurements have shown that Sn (II) had significant impacts on the film morphology which became more porous as a result of the bigger nucleation size of tin. The changes of surface properties of the films was also confirmed by chronoamperometry characteristic (i -t) deposition curve. By optimization of the metal ions concentrations in the electrolyte solution, a copperpoor and zinc-rich kesterite Cu2ZnSnS4 (CZTS) film was synthesized by sulfurization of the deposited CZT film. The solar cell with the CZTS film showed an energy conversion efficiency of 2.15% under the illumination intensity of 100 mW cm -2 .