Biogenic hierarchical porous rice husk SiO₂ samples were prepared from pre-treating rice husk (RH) at low temperatures following TiO₂ sol impregnation and pyrolysis process. The samples were characterized by scanning electron microscopy, X-ray diffraction and energy dispersive spectrometer. Biogenic hierarchical porous structure of untreated RH SiO₂ starts to crack and break down from 800 ℃, whereas TiO₂ grain film is formed on the pore wall and surface of RH SiO₂ after sol impregnation and heat treatment, which enhances the skeleton strength; the biogenic hierarchical porous structure of the rice husk still maintains after firing at 1 400 ℃.