Thermal reaction of titanium tetraisopropoxide and tetraethyl orthosilicate in I.,4-butanediol afforded nanocrystalline silica-modified titanias having large surface area and superior thermal stability. In this study, the thus-obtained silica-modified titanias were treated in an NH3 flow at high temperatures, and their physical and photocatalytic properties were investigated. Compared with NH3-treated TiO2 without silica modification, the NH3-treated silica-modified titanias showed a stronger absorption in the visible region (400-500 nm) and had a larger peak at 396 eV in the N 1s XPS spectrum. These results indicate that a larger amount of nitrogen was stably doped in the silica-modified titania. The obtained products exhibited a high photocatalytic activity for degradation of Rhodamine B and decomposition of acetaldehyde under visible light irradiation.