The objectives of this study were to prepare Ni-Cu/CaO-SiO2 catalysts by a modified polyol process with different preparation conditions and evaluate the feasibility of hydrogen production from methanol steam reforming. CaO-SiO2 materials possess high specific surface areas and CO2 absorption capacities which were synthesized through the sol-gel method to serve as supports. The experimental results of the methanol steam reforming indicated that the highest catalytic activity was achieved when the Ni-Cu/CaO-SiO2 catalyst was prepared under Ar atmosphere at a reduction temperature of 160 degrees C (160-Ar). The 160-Ar catalyst synthesized by this method has a large pore volume and a high mesoporosity. These physical properties contribute to the effective dispersion of metal particles in the 160-Ar catalyst. Increasing the MeOH/H2O ratio was found to promote the water-gas shift reaction and direct methanol decomposition to produce more H-2. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.