In this work, several three-dimensionally ordered macroporous (3DOM) CeO2 having hierarchical pore structure were successfully prepared via a dual 'hard-soft' templating strategy using Ce(NO3)(3)center dot 6H(2)O containing sucrose as the ceria precursor. The resulting CeO2 samples were characterized by N-2 adsorption-desorption analysis, scanning electron microscopy, and transmission electron microscopy, which showed that the hierarchical 3DOM CeO2 possessed interconnected networks of the ordered macropore structures with large mesopores, and both the BET surface area and pore volume increased significantly compared with the conventional 3DOM CeO2. The content of sucrose had a great effect on the textural parameters of the 3DOM CeO2. The improved textural parameters should be attributed to the emergence of mesopores in the interconnected three-dimensional skeleton, which were formed by oxidative removal of carbon produced from carbonization of sucrose. The hierarchical 3DOM CeO2 exhibited a superior performance to the conventional 3DOM or bulk CeO2 when used as supports for Ir catalysts in CO oxidation. (c) 2013 Elsevier B.V. All rights reserved.