Abstract: | Hollow materials with different configurations are of interest due to their unique structural features, which induce interesting properties e.g. catalysis. Here, the synthesis of asymmetrical hollow ball‐in‐tube (HBT) structured CeO2 is reported, which is achieved using a dual template engaged solid–liquid interfacial reaction. In this reaction, the SiO2 sphere (hard template)‐embedded Ce(OH)CO3 nanorod (sacrificial template) composite is first treated with NaOH solution, followed by an acid wash to obtain asymmetrical hollow structured CeO2. Such HBT structured CeO2 is demonstrated to be a good support for Au nanoparticles toward CO oxidation as compared to simple hollow CeO2 nanotubes, leading to significantly increase catalytic activity. |