Upconversion photocatalysts have the potential to extended utilization of sunlight and enhance the photocatalytic performance. A novel hybrid architecture of CeF3/TiO2 nano-sheet film (NSF) was synthesized via a facile one-step microwave-hydrothermal synthesis. The luminescence agent of CeF3 nanodisks were deposited homogeneously on the surface of the TiO2 NSF. The CeF3/TiO2 NSF composite materials show obvious photodegradation of MB under visible light as well as ultraviolet light, resulting in enhanced photocatalytic activity in the UV-vis bands solar spectrum due to the efficient upconversion emissions of CeF3. Additionally, a photocatalytic mechanism of CeF3/TiO2 NSF was proposed.