Well-organized mesoporous SiO2/TiO2 materials with crystallized framework were synthesized. The resultant materials showed high surface area (180–300 m2/g), narrow pore-size distribution (3.5–6 nm), and nanocrystalline framework. The influences of aging conditions on the mesoporous 80TiO2–20SiO2 materials were investigated. The water in the initial solution is beneficial for the mesostructural organization of the as-prepared sample while air moisture (relative humidity) during the aging process plays a key role in the crystallization of the calcined sample. Low aging temperature is another decisive factor to the formation of the mesostructure.