CeO2 hollow microspheres have been synthesized by hydrothermal decomposition reaction of Ce(NO3)3 on the surfaces of silica microspheres. The shell thickness of CeO2 hollow microspheres can be controlled from 20 to 50 nm by adjusting the concentration of Ce(NO3)3 in the reaction solution. The high UV absorption of CeO2 hollow microspheres indicates that this material is suitable as a UV-blocking material.