Two types of polyimide/silica composite films were prepared using sol-gel method through hydrolysis and polycondensation of tetraethoxysilane (TEOS) with the polyamic acid (PAA) and end-capped PAA solution. Samples were characterized by the means of differential thermogravimetry, X-ray diffractometry, scanning electron microscopy, universal test, impedance analyzer, chemical resistance test, etc. All of the PAA/silanol solutions heat-treated at 300℃ for 6h were transformed to polyimide/silica composites. It has been demonstrated that the properties of polyimide/silica composites were affected by the amount of silica addition and the bond type existed between polyimide and silica.