A Cu/CeO2/Al2O3 catalyst (6.6% Cu, 13.8% Ce) based on a structurally organized mesoporous alumina was prepared by a new single-step sol-gel method starting from Al butoxide and Ce and Cu stearates. The sample was characterized by N-2 adsorption, XRD, TPR and Cu dispersion measurements and tested as catalyst for the SRM (methanol steam reforming) and OSRM (methanol autothermal reforming) reactions. The material showed a huge surface area (360 m(2) g(-1)) and resulted to contain very dispersed CeO2 and CuO phases on a poorly crystalline alumina matrix. A highly dispersed Cu metallic phase was obtained after a reductive treatment with H-2. Catalytic tests showed that the unreduced material was fairly active for the OSRM process, but the activity increases appreciably after the pre-reduction treatment. The activity for the OSRM process resulted high, in terms of hydrogen production rate, if compared with data on similar Cu/Ce/Al systems, but the activity for SIRM, in the absence of oxygen was, on the other hand, very low. This behaviour was explained either considering the occurrence of H spillover or the CeO2 assisted oxidation of Cu to Cu+. (C) 2009 Elsevier B.V. All rights reserved.