Macrocellular mesoporous foamlike cerium-tin mixed oxide materials with well-defined porous structure and nanocrystalline frameworks are synthesized through a simple one-step self-assembly process using an amphiphilic triblock copolymer as the single template. The macrocellular pores are synthesized without the addition of any swelling agent or hazardous acids. The final mixed oxide possesses a hierarchically porous structure including macrocellular foam with ultralarge cell size, closed windows, and mesopores on the walls. This indicates that the porous structure can be notably stabilized and improved by the incorporation of Sn in the CeO(2). The materials are expected to be good candidates in catalysis, since the hierarchical porosity enables high surface areas and hence more chemically active sites associated with the mesopores, combined with the high efficiency of mass transport from the macrocellular foam. The catalytic characteristics are discussed in relation to the architectures of the materials, and it is revealed that the macrocellular/mesoporous materials would be an efficient catalyst for CO oxidation.