In this paper, a new simple approach has been developed for the preparation of α-Fe2O3 microspheres by a facile hydrothermal method using PVP as a surfactant. Uniform α-Fe2O3 microspheres could be routinely synthesized through solvothermal approach by controlling the PVP/FeCl3⋅6H2O ratio. The as-obtained α-Fe2O3 microspheres exhibit high efficiency on the decolorization of RhB aqueous solution in the presence of H2O2 at room temperature.