The oxidation states of CeO2 films, deposited on biaxially textured Ni-W(100), c-Al2O3(0001) and Si(100) substrates, were investigated by using X-ray photoelectron spectroscopy (XPS). The CeO2 films were deposited by RF magnetron sputtering under same deposition conditions. X-ray diffraction (XRD) studies of the films revealed that preferred (200) orientation of CeO2 was observed in case of Ni-W substrate while (111) orientation on Al2O3 and Si substrates. The O1s and Ce3d spectra reveal that the films mostly consist of Ce4+ oxidation states with similar to 72.6%, 74.7% and 74.9% on Ni-W, Al2O3 and Si substrates, respectively. The less Ce4+ content in case of Ni-W substrate has been attributed to the migration of oxygen atoms from film to the metallic substrate. The decrease of O2p states in the valence band spectra also in support with the presence of more oxygen vacancies in CeO2/Ni-W compared to that in other substrates. Further, the position of valance band maxima is almost identical (-2.6 eV) for all the deposited films indicating that all films are n-type in nature. (C) 2016 Elsevier B.V. All rights reserved.