Catalysts with high performance are needed to remove the residual CO in the hydrogen streams in order to avoid poisoning Pt anode of proton exchange membrane fuel cells. We herein prepared the CeO2/xCNTs-CuO catalysts that increase the amount of active sites as well as the concentration and distribution of oxygen vacancies at contact interface based on copper-cerium oxides. The CNTs insert in CuO microsphere with one ends, and the other ends extend out the surface. The CeO2 particles uniformly disperse onto the surface of 20CNTs-CuO support to compose an eggshell structure, and this kind of structure can ensure close interaction between CeO2 and CuO to form long contact perimeter. The CNTs play an improvement role on catalytic performance and resistance against CO2 and H2O via increasing the amount of active sites and the concentration of oxygen vacancies in the CeO2/xCNTs-CuO catalysts. CuO microspheres, and they are also inserted the inside of each microsphere with one ends. The other ends of CNTs extend out and twine with CuO on the surface. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.