Nanocrystalline CeO2 films with around 250 nm thickness were deposited on Si (0 0 1) substrates by a facile solgel process with spin coating method. The films are of cubic fluorite structure, and some lattice distortions exist in the film. The phase stability and small change in lattice parameter at different annealing temperatures indicate the good thermal stability of the nanocrystalline CeO2 films. The average grain-size and surface roughness of the films increase with the increase of annealing temperature. The content of Ce3+ and oxygen vacancy is very high in the nanocrystalline CeO2 films, while, the films still remain cubic phase regardless of its high level non-stoichiometric composition. All the annealed samples show two emission bands, and the defect peak centered at similar to 500 nm shows a red-shift. The intensity of the green-emission band increases with the increasing annealing temperature, which might result from the increasing concentration of oxygen vacancies caused by the valence transition from Ce4+ to Ce3+, and it has also been confirmed by the X-ray photoelectron spectroscopy results. This work demonstrates that oxygen vacancy plays an important role on the properties of the nanocrystalline CeO2 film, and it also provides a possible way to control the concentration of oxygen vacancies. (C) 2015 Elsevier B.V. All rights reserved.