A new electrochemical method to prepare photocatalytic TiO2 thin film was developed, by which the TiO2 was electrodeposited on surface of alumina by AC electrolysis in solution consisting of K2 [TiO(C2O4 )2] and C2H2O4. The deposited TiO2 thin film was primarily characterized by X-ray diffraction (XRD), scanning electronic microscopy (SEM) and energy dispersive spectrum (EDS) methods. The photocatalytic properties of this film were also studied by the photocatalytic degradation of methyl orange. The results show that the TiO2 film electrodeposited by this method is mainly in amorphous and with a little crystalline component mixed anatase and rutile. The surface of the alumina prepared by anodic oxidation is porous and the TiO2 electrodeposited on it is scattered and incompact. TiO2 thin film fixed on the surface of alumina shows photocatalytic activity to the degradation of methyl orange.