CeO2@Cu2O nanocomposites were prepared from Cu2O cubes and octahedra by the template-assisted method involving the liquid (Ce(IV))-solid (Cu2O) interfacial reaction. Their compositions, structures, and catalytic activities in CO oxidation were studied in detail. Under the same reaction conditions, CeO2@(CuO)-O-2 nanocomposites prepared from cubic and octahedral Cu2O templates exhibit different compositions and structures. With an increasing amount of Ce(IV) reactant, a smooth CeO2-CuO shell develops on the surface of Cu2O cubes and eventually void cubic core/multishell Cu2O/CeO2-CuOx nanocomposites form; however, a rough CeO2-CuOx shell develops on the surface of Cu2O octahedra, and eventually hollow octahedral CeO2-CuOx nanocages form. The formation of different compositions and structures of CeO2@Cu2O nanocomposites was correlated with the different exposed crystal planes and surface reactivities of Cu2O cubes and octahedra. The catalytic activity of CeO2@Cu2O nanocomposites in CO oxidation depends on their compositions and structures. The most active CeO2@Cu2O nanocomposites become active at 70 degrees C and achieve a 100% CO conversion at 170 degrees C. These results broaden the versatility of Cu2O nanocrystals as the sacrificial template for the fabrication of novel nanocomposites with core/shell and hollow nanostructures and exemplify the morphology effect of Cu2O nanocrystals in liquid solid interfacial reactions with respect to the composition, structure, and properties of nanocomposites prepared by the template-assisted method.