Abstract We investigated by Raman spectroscopy (RS) the crystalline quality of CeO 2 thin films radio frequency magnetron sputtered on n‐type (111) Si substrates from CeO 2 target. The deposition temperature was in the range of 200–800 °C. We also realized structural investigations on CeO 2 layers after Rapid Thermal Annealing (RTA) performed in the range of 750–1000 °C for 30 s under nitrogen atmosphere. So this study displays that a high‐growth temperature and a high post‐growth‐RTA temperature improves the crystalline structure of the film. In fact, the best crystalline quality, which is close to the CeO 2 target taken as a reference, is obtained for a CeO 2 layer deposited at 800 °C and post‐annealed at 1000 °C for 30 s. Copyright © 2008 John Wiley & Sons, Ltd.