The CeO2/CuO and CuO/CeO2 catalysts were synthesized by the hydrothermal method and characterized via XRD, SEM, H-2-TPR, HRTEM, XPS and N-2 adsorption-desorption techniques. The study shows that the rod-like structure is self-assembled CeO2, and both hydrothermal time and Ce/Cu molar ratio are important factors when the particle-like CeO2 is being self-assembled into the rod-like CeO2. The CuO is key active component in the CO-PROX reaction, and its reduction has a negative influence on the selective oxidation of CO. The advantage of the inverse CeO2/CuO catalyst is that it still can provide sufficient CuO for CO oxidation before 200 degrees C in the hydrogen-rich reductive gasses. The traditional CuO/CeO2 catalyst shows better activity at lower temperature and the inverse CeO2/CuO catalysts present higher CO2 selectivity when the CO conversion reaches 100%. The performance of mixed sample verifies that they might be complementary in the CO-PROX system. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.