TiO2 nanofiber films (TiO2 NFF) with visible light scattering ability were prepared using a hydrothermal method. Au nanoparticles (Au NPs) were then deposited on the surface of TiO2 film using a microwave-assisted chemical reduction process. An overlapped light-trapping phenomenon was observed in Au/TiO2 NFF due to the light-scattering nanostructures of TiO2 film and the localized surface plasmon resonance (LSPR) of Au NPs. The MB degradation over the composite films is much faster than that of pure TiO2 film. The enhanced photocatalytic activity is primarily attributed to the charge transfer property and the overlapped light-trapping nanostructures of Au/TiO2.