Highly active TiO 2 /Fe–TiO 2 composite photocatalysts with a p–n heterojunction structure have been prepared by mixing hydrothermal-derived TiO 2 and Fe–TiO 2 nano-powders followed by grinding and drying. These photocatalysts were characterized by XPS, XRD, TEM, BET, UV–vis and Fluorescence spectroscopy, and their photocatalytic activities were evaluated by the decolorization rate of methyl orange under UV irradiation. TiO 2 /Fe–TiO 2 composite photocatalysts were generally shown to have a much higher photocatalytic destruction rate than pure TiO 2 , mainly due to electrostatic-field-driven electron–hole separation in TiO 2 /Fe–TiO 2 composites. The best TiO 2 /Fe–TiO 2 composite photocatalyst with mass ratio TiO 2 :0.5at%Fe–TiO 2 of 12:1 showed approximately 3.8 times higher photocatalytic activity than undoped TiO 2 .