The performance of different Cu/CeO2/Al2O3 catalysts of varying compositions is investigated for the oxidative steam reforming of methanol (OSRM) in order to produce the hydrogen selectively for polymer electrolyte membrane (PEM) fuel cell applications. All the catalysts were prepared by co-precipitation method and characterized for their surface area, pore volume and oxidation-reduction behavior. The effect of various operating parameters studied are as follows: reaction temperature (200-300 degrees C, contact-time (W/F=3-15 kg(cat) s mol(-1)) and oxygen to methanol (O/M) molar ratio (0-0.5). The steam to methanol (S/M) molar ratio= 1.5 and pressure= 1 atm were kept constant. Among all the catalysts studied, catalyst Cu-Ce-Al:30-20-50 exhibited 100% methanol conversion and 179 mimol s(-1) kg(cat)(-1) hydrogen production rate at 280 degrees C with carbon monoxide formation as low as 0.19%. The high catalytic activity and hydrogen selectivity shown by ceria promoted Cu/Al2O3 catalysts is attributed to the improved specific surface area, dispersion and reducibility of copper which were confirmed by characterizing the catalysts through temperature programmed reduction (TPR), CO chemisorption, X-ray diffraction (XRD) and N-2 adsorption-desorption studies. Reaction parameters were optimized in order to produce hydrogen with carbon monoxide formation as low as possible. The time-on-stream stability test showed that the Cu/CeO2/Al2O3 catalysts were quite stable. (C) 2007 Elsevier B.V. All rights reserved.