Rh/CeO2 catalysts submitted to different H2 reduction, Ar+ sputtering, and oxidation treatments have been studied by X-ray photoelectron (XPS) and 1H nuclear magnetic resonance (NMR) spectroscopies. Depending on the reduction temperature, two stages have been identified in the reduction of the catalyst: below 473 K, reduction increases the amount of OH and Ce3+ species; above this temperature, reduction produces oxygen vacancies at the surface of the support. Volumetric and microcalorimetric techniques have been used to study hydrogen adsorption on the catalyst, and 1H NMR spectroscopy was used to differentiate hydrogen adsorbed on the metal from that adsorbed on the support. From 1H NMR and TEM results, the main metal particle size (38 A) in the Rh/CeO2 catalyst has been estimated. The influence of the support reduction on the metal adsorption capacity has also been investigated, showing that formation of oxygen vacancies at the metal-support interface enhances the electronic perturbation and decreases the hydrogen adsorption on metal particles. The comparison of data reported on catalysts of high and low surface area supports has shown that both processes are shifted to higher temperatures in the Rh/CeO2 catalyst of lower surface area.