TiO 2 is an attractive catalyst for the photocatalytic degradation of organic pollutants. However, owing to its large band gap, it can only be activated by ultraviolet (UV) light, which constitutes a small portion of solar energy. Therefore, there has been significant interest in extending its light absorption range from UV to visible light. In this study, fluorinated TiO 2 hollow spheres (FTHSs) were prepared via a rapid and simple wet chemical process using ammonium hexafluorotitanate, and then FTHS/WO 3 heterostructures with different weight ratios of the FTHS and WO 3 nanoparticles were synthesized via a simple wet impregnation method. The formation of the hybrid structure was confirmed by various characterization techniques. The photocatalytic activity of the synthesized photocatalysts in the photodegradation of rhodamine B, a model pollutant, was evaluated under visible light irradiation. The FTHS/WO 3 heterostructures exhibited significantly improved photocatalytic activity compared to the bare FTHS or WO 3 nanoparticles. The photodegradation efficiency of the FTHS/WO 3 heterostructure in the present study was up to 0.0581 min −1 . Detailed mechanisms that lead to the enhanced photocatalytic activity of the heterostructures are discussed. In addition, comparative experiments reveal that the photodegradation efficiency of the FTHS/WO 3 heterostructure under visible light irradiation is superior to that of the P25/WO 3 heterostructure prepared from the commercially available TiO 2 catalyst (P25) via the same impregnation method.