A series of CuO/CeO2 and inverse CeO2/CuO catalysts are prepared by the surfactant-templated method and characterized via XRD, HRTEM, H-2-TPR, SEM, XPS, in situ XRD, in situ UV-Vis and N-2 adsorption-desorption techniques. It is found that there are two kinds of surface sites in the CuO-CeO2 system, including CuO surface sites for CO chemisorption and CeO2 surface sites with oxygen vacancies for oxygen sorption. The active sites for CO oxidation are located on the contact interface of two-kind surface Sites and the lattice oxygen can make a significant contribution to the CO-PROX reaction. The resistance to H2O and CO2 is related to BET surface area, the crystallite sizes of CuO and the reduction behavior of catalysts. The Ce4Cu4 and Ce4Cu1 catalysts exhibit the best resistance against H2O and CO2. (C) 2014 Elsevier B.V. All rights reserved.