The synthesis of ZnO/CuO films on ITO substrate was realized in two steps, first ZnO was deposited electrochemically and then CuO nanoparticles were precipitated with help of spin coating technique. ZnO nanorods were obtained in aqueous Zn(NO3)(2)solution, in presence of KCl as capping agent. Spin coating technique yielded CuO nanoparticles on these nanorods, particle size was employed by copper (II) acetate and ethanolamine in 2-methoxyethanol. In addition, field emission scanning electron microscopy (FESEM) and energy dispersive X-ray spectroscopy studies were also realized for understanding the structure. UV-Visible spectrophotometer study results revealed that the bandgap value of bilayered structure was governed by presence of CuO nanoparticles. Mott-Schottky analysis was realized for characterization of prepared semiconductor materials, which indicated to + 0.571 for ZnO/CuO(3), while these values were + 0.532 V and - 0.360 V for CuO and ZnO, respectively. Electrochemical measurements were realized with help of solar simulator, for testing photocatalytic activity of ZnO/CuO as photocathode material, in aqueous solution.