With the approach of anodic oxidation, TiO2/Ti film doped with Cu2+ was produced in H2SO4 electrolyte mixed with CuSO4. The surface morphology and the roughness of the films were studied with atomic force microscopy. The phase composition of the films was studied by X-ray diffraction. The photocatalytic activity of the films was compared through the photocatalytic degradation rate of phenol. The relations of the photocatalytic activity to the concentration of Cu2+, the microstructure and the surface roughness of the film were investigated. The results showed that Cu2+ increased the surface roughness and restrained the growth of crystal. In addition, the phenol in aqueous solution was successfully photodegraded under visible light irradiation by Cu2+-TiO2/Ti film. The composition and structure of the film affected the catalytic activity greatly. Compared with TiO2/Ti film, the recombination rate of e- and h+ of Cu2+-TiO2/Ti film was decreased.