Polyimide and hybrid polyimide-siloxane were synthesized by polycondensation, imidization, and sol-gel reaction. The polyimides were prepared from pyromellitic dianhydride (PMDA) and 4,4-oxydianiline (ODA) in N-methyl-2-pyrollidone (NMP). Trimethoxyvinyl silane (TMVS) was used as a source of silica. Their surface morphologies, structures and thermal performances were determined using scanning electron microscopy (SEM), infrared spectroscopy (IR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results showed that the silica particles were finely and rather homogeneously dispersed in polymers. The glass transition temperature (T-g) of hybrid membrane materials increased with the increasing silica content. TGA analysis showed that polyimides were thermally stable with silica. Modified polyimide-siloxane films, thermal characteristics were found to be better than the polyimide films without silica. Copyright (C) 2006 John Wiley & Sons, Ltd.