The surface structure and reactivity of vanadia supported on ceria catalysts were studied by Raman spectroscopy and methanol adsorption and temperature-programmed surface reaction (TPRS) of the adsorbed species monitored in situ by infrared spectroscopy. Monomeric and polymeric vanadia surface species and CeVO4 were identified on the catalysts. Methanol adsorption reveled that mostly reduced Ce3+ sites are present in the surface of the catalysts, produced as a result of the reductive solid reaction of VOx species with the ceria surface. Adsorbed methanol/methoxy decomposed stepwise to formate and, finally, carbonate/carbon dioxide. The reactivity is linked to interphase sites, Ce-O-V, which could favor the abstraction of hydrogen during the methoxy transformation to formates. (C) 2015 Elsevier B.V. All rights reserved.