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This paper focused on the preparation and characterization of a pure TiO2 monolith. The preparation method is based on the sol-gel technique using tetrabutyl titanate as precursors. By controlling the hydrolysis of tetrabutyl titanate and the rate of gel drying, transparent TiO2 gel-monoliths are obtained at room temperature. The TiO2 gel-monoliths prepared in this manner have a mean pore diameter about 4.4 nm, specific surface area 332.8 m2g−1 and more than 57.6% porosity, especially, the TiO2 gel-monoliths are not amorphous but crystalline, anatase phase. It retains a surface area and a porosity of about 90.5 m2g−1 and 45.6%, respectively, after the heat treatment at 500 °C for 2 h. And XRD, TEM and N2 adsorption isotherm analysis indicate that particle growth is the main influencing factor of the specific surface area and porosity from room temperature to 500 °C, but from the heat treatment temperature higher than 500 °C, the densification assisted by anatase to rutile phase transition become the main role to influence the specific surface area and porosity.