CeO2 and Ce/V mixed oxide thin films prepared by sol-gel deposition and annealed in an air or argon atmosphere have been studied by chronocoulometry and by XAFS (X-ray absorption fine structure). Multielectron photoexcitations (MPE), well known to pervade XAFS spectra of Ce making the analysis of structural parameters unreliable, are removed with the help of the atomic absorption background, determined on simple Ce compounds. Distinct MPE estimates for Ce3+ and Ce4+ ions are used. In the analysis of the recovered pure XAFS signal, the degree of disorder is found to depend on the Ce/V molar ratio and on the heating atmosphere. The disorder correlates with charge capacity of films, both increasing with vanadium content and V4+/V5+ molar ratio. (C) 2003 Elsevier B.V All rights reserved.