The Cu-based catalysts with different supports (CeO2, ZrO2 and CeO2-ZrO2) for methanol steam reforming (MSR) were prepared by a co-precipitation procedure, and the effect of different supports was investigated. The catalysts were characterized by means of N-2 adsorption-desorption, X-ray diffraction, temperature-programmed reduction, oxygen storage capacity and N2O titration. The results showed that the Cu dispersion, reducibility of catalysts and oxygen storage capacity evidently influenced the catalytic activity and CO selectivity. The introduction of ZrO2 into the catalyst improved the Cu dispersion and catalyst reducibility, while the addition of CeO2 mainly increased oxygen storage capacity. It was noticed that the CeO2-ZrO2-containing catalyst showed the best performance with lower CO concentration, which was due to the high Cu dispersion and well oxygen storage capacity. Further investigation illuminated that the formation of CO on CuO/ZnO/CeO2-ZrO2 catalyst mainly due to the reverse water gas shift. In addition, the CuO/ZnO/CeO2-ZrO2 catalyst also had excellent reforming performance with no deactivation during 360 h run time and was used successfully in a mini reformer. The maximum hydrogen production rate in the mini reformer reached to 162.8 dm(3)/h, which can produce 160-270 W electric energy power by different kinds of fuel cells. Copyright (c) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.