The CuO supports with different morphology were prepared using the precipitation method. The inverse CeO2/CuO catalysts were synthesized by the impregnation method, and characterized via XRD, H-2-TPR, SEM, TEM, XPS and N-2 adsorption-desorption techniques. The study showed that CO oxidation took place at the interface of CeO2 CuO catalysts. The CeO2/CuO catalysts maintained their morphologies, structure and the length of periphery at the CeO2 CuO interface in the hydrogen-rich reaction gasses during the reaction. The two-dimensional and homogeneous petal morphology of support was most favorable for the formation of long periphery at the CeO2 CuO interface, therefore the CeO2 supported on the CuO with petal morphology presented good catalytic activity. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.