Polyimide-silica hybrid materials have been prepared through the sol-gel process by mixing various proportions of tetraethoxysilane (TEOS) with polyamic acids (PAAs). Two types of PPAs were employed. The first was obtained by reacting an equimolar mixture of oxydianiline (ODA) and pyromellitic dianhydride (PMDA) in dimethylactamide (DMAc) as solvent. The second was prepared using a mixture of ODA and 2,2-Bis(3-amino-4-hydroxyphenyl) hexafluoropropane (6F-OHDA) in molar ratio 9: 1, respectively and reacting with a stoichiometric amount of PMDA in DMAc. Polyamic acids were converted to polyimides and a sol-gel reaction proceeded simultaneously by heating the hybrid films to 300 degrees C. The hydroxyl groups from 6F-OHDA allows the secondary bonding between the polyimide and growing silica phase and thus retard the gross phase separation. Only the 10 mol% addition of 6F-OHDA in the polyimide chain resulted in a drastically different microstructure for the resulting hybrids. SEM, stress-strain analysis, temperature variation of storage and loss modulus, and thermal stability were used to characterize the hybrid materials. Properties of both types of hybrids have been compared and related to the two different types of structures of polyimides used in the preparation of the hybrids.