Iron-doped TiO2 photocatalyst powders were prepared by the sol–gel method and characterized by Brunauer–Emmett–Teller (BET)-specific surface area, scanning electron microscopy (SEM), X-ray diffraction (XRD), and Ultraviolet–Visible (UV-Vis) spectroscopy. Fe3+ doping in the TiO2 decreases the crystal grain size, increases the specific surface areas of powders, extends the absorption to visible light regions (400~500 nm), and lowers the photocatalytic activity for methylene blue (MB) degradation under UV irradiation. The photocatalytic degradation of MB in water was investigated as a function of the Fe3+ content in TiO2. It was found that under the irradiation of visible light, a small amount of Fe3+ dopant in TiO22 powders could obviously enhance the photocatalytic activity. When the Fe3+ content was in the range of 0.03–0.1 mol%, the photocatalytic activity of the samples was higher than that of undoped TiO2. Appropriate content of Fe-doping is an effective means to improve the photocatalytic activity of TiO2 for MB degradation under visible light irradiation.