An efficient solvothermal method was developed to prepare CeO2 microcrystals with different shapes using a polyol-ethanol mixed solvent as the reaction medium. The as-synthesized product was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and UV-vis diffuse reflectance spectroscopy (DRS). It was found that different kinds or amounts of polyols and the concentration of oleic acid have significant impacts on the well-defined CeO2 microcrystals. The as-synthesized CeO2 microcrystals displayed different optical absorption properties and different photocatalytic performances for the degradation of Rhodamine B (RhB) under UV and visible light irradiation, which was used to model sunlight. (C) 2013 Elsevier B.V. All rights reserved.