Three dimensionally ordered (3DOM) copper-ceria based catalysts (CeO2-CuO, CeO2-CuO -Fe2O3, and CeO2-CuO-CO3O4) with diverse Ce/Cu atomic ratios and different doping amounts of Fe2O3 and CO3O4 are synthesized via a precursor thermal decomposition-assisted colloidal crystal templating method. The as-obtained CeO2-CuO, CeO2-CuO Fe2O3 and CeO2-CuO-CO3O4 catalysts possess three dimensionally ordered macroporous structures. And their particle sizes, chemical compositions, and surface elemental states are investigated according to the variations of Ce/Cu atomic ratios and doping amounts of Fe2O3 and CO3O4. The catalytic performance of CO preferential oxidation in H-2-rich gases over 3DOM CeO2-CuO, CeO2 CuO-Fe2O3, and CeO2-CuO-CO3O4 catalysts are mainly relevant to their particle sizes, chemical compositions, surface states, and synergetic interactions between different components. By modulating the Ce/Cu atomic ratios and the doping amounts of Fe2O3 and CO3O4, the superior catalytic performance of 3DOM CeO2-CuO catalysts with high CO conversion, CO2 selectivity and longer-term stability in a wide operation temperature window is achieved. This synthetic strategy provides a new methodology for the fabrication of 3DOM structured highly efficient catalysts, which would be very useful in the actual working conditions for proton exchange membrane fuel cells and water-gas shift reactions. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.