To efficiently degrade printing and dyeing wastewater at low costs, Cu2O/Al2O3 catalyst was prepared by electrochemical method. Under its combined action with H2O2, photocatalytic degradation of methyl orange solution, as simulated wastewater, was carried out. With the aid of X-ray diffractometer, X-ray microanalysis system and scanning electron microscope, the structure and composition of catalyst film were designed by adjusting the electrochemical parameters, and the performance of photocatalyst was evaluated by the degradation rate of methyl orange. It was found that after anodizing aluminum alloy for 2 h in a 2 mol/L H2SO4 solution under a voltage of 15 V, alumina film with reasonable pore size distribution could be prepared on the alloy surface. By electroplating the film in a 0.01 mol/L CuSO4 solution at 5°C, and then hydrothermally treating it at 200°C, the Cu2O/Al2O3 photocatalyst could be obtained. The prepared Cu2O/Al2O3 and 10% H2O2 were used jointly as photocatalyst to degrade 10 mg/L methyl orange solution for 480 min, which achieved a methyl orange degradation rate of up to 82.1%.