A commercial route has been developed to synthesize submicrometer titanium nitride from titanium dioxide/phenolic resin composite. The phenolic resin served as the carbon source and the titanium dioxide served as titanium source to produce titanium nitride in flowing ultrahigh purity N-2 atmosphere at 1373-1773 K. Titania was embedded in a continuous phenolic resin dispersant. X-ray diffraction and field emission scanning electron microscope were employed to characterize the phase composition, microstructure and reaction mechanism. It was found that the reaction sequence was TiO2 -> Ti4O7 -> Ti3O5 -> TiN and the whole formation process was consisted of chemical synthesis reaction process firstly and the following recrystalline-physical process. The optimal conditions to prepare titanium nitride powders were determined: the molar ratio of titanium dioxide to phenolic resin is 1:0.5; thermostatic temperature is 1773 K, and thermostatic time is 2 h. The stepped structure on the surface of product formed due to recrystallization. The particle size of the obtained titanium nitride powders is about 0.5 mu m.