A facile sol-gel methodology based on the glycerol-gel reaction was used to prepare single-phase BiFeO3 crystallites. The particle size and morphologies of BiFeO3 crystallites were characterized by field-emission scanning electron microscope and transmission electron microscope. X-ray diffraction results indicated that single-phase and well-crystallized BiFeO3 has been synthesized at the temperature as low as 400 degrees C. In present work, single-phase BiFeO3 can be formed at lower temperature and less organics is required, furthermore, the process is simple and easy to control.