A surface study of electrodeposited cerium oxide based coatings is presented. Different surface analytical techniques were used in order to obtain complementary information to fully characterize such complex systems. X-ray Photoelectron Spectroscopy was used as the main technique to determine the surface composition of the coating. The analysis of the core level peaks of the elements provides additional information about the functional groups present on the surface. A mixture of Ce (III) and Ce (IV) was found in the coating and their proportion was calculated at different depths. The analysis of the O 1s core level peak revealed a triple structure whose origin will be discussed. To support the results obtained, electron stimulated desorption was performed. The study was completed with Auger electron spectroscopy and Raman spectroscopy, both techniques having different surface sensitivities. From all these results, it is derived that incomplete electrochemical reactions occurred during the growth of the coatings. This led to rather complex compositions, in which defective cerium oxides are the major species. In addition, hydroxides, carbonates and nitrates are also present, together with adsorbed water. (C) 2011 Elsevier B. V. All rights reserved.