The principle and preparation process of organic silicone/SiO2 hybrid materials prepared by the method of sol-gel were described. The applied research of organic silicone/SiO2 hybrid materials in the field of heat-resistant materials, corrosion protection and optical materials were summarized. The organic silicone/SiO2 hybrid materials prepared by the sol-gel as an all-silicon system combined the advantage of the organic silicone and nano-SiO2, which render it a promising material.