Mesoporous SiO2–TiO2 was synthesized by the sol–gel method using Si(OC2H5)4, Ti(OC2H5)4, and stearyltrimethylammonium chloride. By using acetylacetone as the capping agent of Ti(OC2H5)4, homogeneous SiO2–TiO2 composite was obtained. Spherical mesoporous SiO2–TiO2 was also synthesized by the sol–gel method using W/O emulsion under microwave irradiation. The specific surface area of these mesoporous SiO2–TiO2 materials decreased when the Ti/Si molar ratio was higher than 0.1, which indicated that Ti was homogeneously distributed in mesoporous SiO2 matrix at Ti/Si ≦ 0.1. The photocatalytic activity of mesoporous SiO2–TiO2 materials was investigated by the degradation of methylene-blue in water under UV light irradiation. Mesoporous SiO2–TiO2 was effective for the adsorption–decomposition of methylene-blue.