The purposes of this study were to prepare a copper catalyst by the microwave-heated polyol (MP) process and subsequently to evaluate the feasibility of the preferential oxidation of CO (CO-PROX) in excess H-2. A CeO2-TD support was firstly prepared by the thermal decomposition from Ce(NO3)(3)center dot 6H(2)O precursor. For comparison, commercial ceria (CeO2-C) and activated carbon (AC) selected as support materials. Experimental results of CO-PROX indicated that the highest catalytic activity is achieved when the Cu/CeO2-TD used as catalysts. Correlating to the characteristic results, it is found that the CeO2-TD support prepared by the thermal decomposition has a large surface area and high mesoporosity; these properties contribute to the easy adsorption of pollutants and the effective dispersion of metal particles. Further investigation of feed composition found that Cu/CeO2-TD catalysts possess 100% CO conversion even existence of CO2 and H2O in H-2-rich streams at 150 degrees C. Besides, a decrease in CO conversion was clearly observed above 175 degrees C for Cu/CeO2-TD catalysts due to the reverse water gas shift reaction tending to reform CO from CO2 and H-2. Copyright (c) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.