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TiO2 nanotube array films were prepared on Ti substrates by a potentiostatic anodization method. Then, MoO3 nanoparticles were deposited on the TiO2 films by a pulse current deposition technique. The properties of the prepared films were characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-Vis spectrophotometry, photoluminescence and photoelectrochemical measurements. Besides, the photogenerated cathodic protection performances of the composite films were investigated by recording the potential change of 403 stainless steel coupled to the films under white light illumination. The result showed that the absorption edge of the MoO3/TiO2 composite film was red-shifted compared with the pure TiO2 nanotube film, and the photochemical performance of the composite film was impoved. After 403 stainless steel in a corrosive solution with 0.5 M NaCl was coupled to the MoO3/TiO2 composite film under white light illumination, its potential decreased by 540 mV, showing an improved photogenerated cathodic protection effect on the steel.