Highly ordered TiO2 nanotube array(TNA) films are fabricated by using an anodic oxidation method. Au nanoparticles(NPs) films are decorated onto the top of TNA films with the aid of ion-sputtering and thermal annealing. An enhanced photocatalytic activity under ultraviolet C(UVC, 266 nm) light irradiation is obtained compared with that of the pristine TNA, which is shown by the steady-state photoluminescence(PL) spectra. Furthermore, a distinct blue shift in the nanosecond time-resolved transient photoluminescence(NTRT-PL) spectra is observed. Such a phenomenon could be well explained by considering the competition between the surface photocatalytic process and the recombination of the photo-generated carriers. The enhanced UV photocatalytic activities of the Au–TNA composite are evaluated through photo-degradation of methyl orange(MO) in an aqueous solution with ultraviolet–visible absorption spectrometry. Our current work may provide a simple strategy to synthesize defect-related composite photocatalytic devices.