Inspired by natural wood, novel Ce0·7Zr0·3O2 catalyst with hierarchical porous structure, W–CeZr, was fabricated using wood template method by utilizing catheter pores and pits in poplar. W–CeZr catalyst was then used for selective catalytic reduction of NO with NH3 for the first time. Compared with conventional Ce0·7Zr0·3O2 catalyst (C–CeZr), W–CeZr catalyst mimicked biological microstructure of wood and exhibited much greater low-temperature activity than C–CeZr, i.e., NO conversion for W–CeZr was 100% in the range of 250–350 °C, while that for C–CeZr was only 58.1% at 250 °C. Based on a series of characterization techniques, this effect can be attributed to an increase in surface area (m2·g−1), enrichment of Ce3+, and enrichment of surface-active oxygen species by 133.7%, 60%, and 59.5% compared to C–CeZr, respectively. In situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy results show that more activated reactants were present on the surface of W–CeZr because of its stronger surface acidity, as well as redox and oxygen storage abilities.