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The Cu/Ti composite coatings were prepared by the mechanical ball milling, the CuO/TiO2 and Cu2O/TiO2 composite photocatalytic films were obtained by the subsequent oxidation process. The microstructure of the composite films was analyzed by X-ray Diffraction (XRD）and scanning election microscope (SEM). The photocatalytic activity was evaluated, the effects of ball milling time on the formation of the Cu/Ti coatings were investigated, and the effects of the oxidation temperature and oxidation atmosphere on microstructure and photocatalytic activity of the films were studied. The results illustrate that the ball milling time has significant effects on the formation of the coatings and the coatings are continuous and compact by ball milling for 15 h. The photocatalytic activity of the CuO/TiO2 composite films is increased first and then decreased with the oxidation temperature increases, and the photocatalytic activity is the best at 500 °C. The CuO/TiO2 composite films are obtained by the oxidation of Cu/Ti coatings at 500 °C for 15 h in the air, while the Cu2O/TiO2 composite films are oxidized in carbon atmosphere. Photocatalysis efficiency of the films is obviously enhanced with the help of the p-n junction heterostructure in the Cu2O/TiO2 composite films.