A very simple and controllable approach was proposed to synthesize novel Fe(OH)3/TiO2 nanoparticles. Compared with neat TiO2, the Fe(OH)3/TiO2 increased the rate of the photocatalytic degradation of methyl orange at pH 6.0 by more than five times, showing photocatalytic activity as excellent as P25. This enhancing effect is mainly attributed to the ferric hydroxide deposits as the electron scavenger and the enriched surface hydroxyl groups.