La-doped TiO2−xFx (La–TiO2−xFx) powders were prepared by the sol–gel method. X-ray diffraction results showed that La efficiently inhibited grain growth. X-ray photoelectron spectroscopy spectra revealed that La2O3 and O–Ti–F bonds have formed, the La2O3 maintained the high surface area of TiO2−xFx after calcination at a temperature above 500°C, while the O–Ti–F bonds increased the oxidation potential of the photogenerated hole in the valence band. The UV-vis spectroscopy of the La–TiO2−xFx showed that the presence of intraband gap states was likely responsible for its absorption of visible light. When the molar ratios of La and F to Ti were 1.5:100 and 5:100, respectively, and calcined at 500°C, the photocatalytic degradation rate of methylene blue over La–TiO2−xFx was about 1.5 times higher than that of F-doping TiO2.