Using the ultrasonic pyrolysis method, spherical SiO2 powders were synthesized from aqueous SiO2 sol as a starting material. The effects of pyrolysis conditions such as reaction temperature, SiO2 sol concentration, and physical properties of precursor were investigated for the morphologies of the resulting SiO2 powders. The particle size, shape, and crystallite size of the synthesized SiO2 powders were demonstrated according to the pyrolysis conditions. Generally, the synthesized SiO2 particles were amorphous phase and showed spherical morphology with a smooth surface. It was revealed that increased crystallite size and decreased spherical SiO2 particle size were obtained with increases of the pyrolysis reaction temperature. Also, quantity of spherical SiO2 particles decreased with the decrease in the concentration and surface tension of the precursor.