Nanocrystalline titanium dioxide was prepared via aerosol pyrolysis of titanium alkoxide precursor at 200–580 °C in air and in nitrogen atmospheres. Powders were characterized by x-ray diffraction, thermogravimetric analysis, Brunauer–Emmett–Teller analysis, scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, x-ray fluorescence, Raman and infrared spectroscopy, and Berner-type low-pressure impactor. The anatase phase transition was initiated at 500 °C in nitrogen and at 580 °C in air. Under other conditions amorphous powders were observed and transformed to nanocrystalline TiO2 via thermal postannealing. In air, smooth and spherical particles with 2–4-μm diameter were formed with an as-expected tendency to convert to rutile in the thermal postannealings. In nitrogen, a fraction of the titanium tetrabutoxide precursor evaporated and formed ultrafine particles via the gas-to-particle conversion. At 500 °C thermally stable anatase phase was formed in nitrogen. A specific surface area as high as 280 m2 g−1 was observed for an as-prepared powder.