CeO2thin films have been deposited on single-crystal MgO(001) substrates by the pulsed laser ablation technique. The composition, phase formation, crystalline quality of the films, and the film/substrate orientation relationships have been analyzed by the complementary use of Rutherford backscattering spectrometry and X-ray diffraction analysis. The films grown under vacuum at temperatures lower than 700°C are not crystalline. The quality of the films is largely improved at higher temperatures. So, highly textured (00l) CeO2films are grown at 750°C under vacuum with a crystallinity comparable to that of monocrystals. The film/substrate epitaxial relationships present well defined in-plane orientations at 0° and at 45°. The relative amount of film grown in each one of these orientations is largely determined by the growth conditions.