Alpha-Fe2O3 hollow micospheres have been successfully synthesized by solvothermal method at 200 degrees C. The synthesized products are characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and the nitrogen adsorption-desorption isotherm technique. The alpha-Fe2O3 hollow microspheres have an average diameter of 2-3 microm, the shell consists of numerous aligned nanorods with length of about 200-400 nm. The effects of solvent and reaction time have been studied. The Ostwald ripening mechanism is proposed to account for the formation of alpha-Fe2O3 hollow microspheres. Because of the porous hollow microstructure and large specific surface area, the microspheres were found to be effective sorbents for the removal of Cr(VI) ions from wastewater.