A Cu/CeO2/Al2O3 catalyst prepared by a single-step sol–gel method was studied for methanol steam reforming (SRM) to gain information on the oxidation state of Cu and the role of oxidized Cu species. The catalyst was tested in a new laboratory-made flow apparatus that allowed on-line analysis of the products and measurement of the oxidation state and dispersion of Cu in situ. The catalyst pre-reduced in H2 was more active and selective than the not pre-reduced one. The oxidation state, evaluated after SRM tests, suggested the presence of a layer of oxygen atoms on the metallic Cu surface. Treating the prereduced catalyst with H2O vapour at 250 ◦C caused dissociative H2O chemisorption and led to a partial oxidation of Cu. The H2O oxidized sa...