Visible light responsive nitrogen-doped titania nanocrystals were prepared by "Homogeneous Precipitation-Solvothermal Process" in TiCl3-hexamethylenetetramine (C6Hi2N4) mixed solution. The phase composition, crystallinity, microstructure and specific surface area of titania greatly changed depending on pH,solvent and temperature. The titania powders prepared in TiCl3-hexamethylenetetramine aqueous solutions at pH 1～6 and 190℃ for 2 h consisted of single phase of brookite and that prepared at pH 9 was single phase of rutile. On the other hand, the sample prepared in the presence of methanol at pH 9 consisted of single phase of anatase. All titania powders prepared in the present study were yellow and showed excellent visible light absorption property and photocatalytic ability for NO destruction under irradiation of the visible light (λ＞510nm). The photocatalytic activity of the sample possessing similar specific surface area was in the order anatase ＞ brookite ＞ rutile. The photocatalytic activity of nitrogen doped titania under irradiation of visible light (λ＞510 nm) slightly decreased with increasing calcination temperature up to 600℃ and then greatly decreased at 800 C. The visible light responsive photocatalytic activity of rutile titania nanoparticles could be improved by forming nanocomposite with layered tetratitanate possessing high specific surface area via a delamination-reassembly process of K2Ti4O9 combined with planetary ball-milling.