A series of Au–TiO2/ITO films with nanocrystaline structure was prepared by a procedure of photo-deposition and subsequent dip-coating. The Au–TiO2/ITO films were characterized by X-ray diffraction, scanning electronic microscopy, electron diffraction, X-ray photoelectron spectroscopy, and UV–VIS diffuse reflectance spectroscopy to examine the surface structure, chemical composition, the chemical state of metal, and the light absorption properties. The photocatalytic activity of the Au–TiO2/ITO films was evaluated in the photocatalytic (PC) and photoelectrocatalytic (PEC) degradation of bisphenol A (BPA) in aqueous solution. Compared with a TiO2/ITO film, the degree of BPA degradation using the Au–TiO2/ITO films was significantly higher in both the PC and PEC processes. The enhancement is attributed to the action of Au deposits on the TiO2 surface, which play a key role by attracting conduction band photoelectrons. In the PEC process, the anodic bias externally applied on the illuminated Au–TiO2/ITO film can further drive away the accumulated photoelectrons from the metal deposits and promote a process of interfacial charge transfer.