In consideration with the highly ordered hexagonal close-packed pores of anodic aluminum oxide (AAO) and the enhanced metal-support interactions in core-shell structured units, herein, hierarchical Pd@CeO2/AAO was developed and evaluated for catalytic combustion of low concentrated toluene and methane. The special configuration demonstrates a superior performance. A toluene conversion of (>) 99% at 250 degrees C is achieved over Pd@CeO2/AAO with a low Pd loading amount of 0.28 wt.%. No activity loss or Pd agglomeration is observed after a 50 h stability test on 0.28 wt.% Pd@CeO2/AAO, while obvious Pd agglomeration is found on the conventional particle catalyst. Both the monolith-like nanotube array structure of AAO, which facilitates Pd@CeO2 distribution and reactant diffusion, and the stable PdO state in core-shell Pd@CeO2 nanostructure together contribute to the promising performance of Pd@CeO2/AAO.