Nanocrystalline SnO2 was synthesized by direct mixing and grinding of SnCl4·5H2O and NaOH at roomtemperature, followed by calcination at different temperatures for different times in air. Product samples were characterized by X-ray diffraction and transmission electron microscope, revealing that the amorphous precursor SnO2 was transformed to crystals at 200 ℃ for 3 h, and that the average particle size increased upon raising the calcining temperature or prolonging the calcining time. The mechanism of the phase transformation of the products is discussed.