Polyimide-silica (PI-SiO2) hybrids were prepared from a novel polyimide (PI), derived from pyromellitic dianhydride (PMDA), 1,6-bis(4-aminophenoxy)hexane (synthesized) and 4,4′-oxydianiline. SiO2 networks (5–30 wt%) were generated through sol–gel process using either tetraethylorthosilicate (TEOS) or a mixture of 3-aminopropyltriethoxysilane-PMDA-based coupling oligomers (APA) and TEOS. Thin, free standing hybrid films were obtained from the respective mixtures by casting and curing processes. The hybrid films were characterized using Fourier transform infrared, 29Si nuclear magnetic resonance (NMR), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectrometry and atomic force microscopy (AFM) techniques. 29Si NMR results provide information about formation of organically modified silicate structures that were further substantiated by FE-SEM and AFM micrographs. Contact angle measurements and thermogravimetric thermograms reveal that the addition of APA profoundly influences surface energy, interfacial tension, thermal stability and the residual char yield of modified hybrids in comparison to those obtained by mixing only TEOS. It was found that reduced particle size, efficient dispersion and improved interphase interactions were responsible for the eventual property enhancement. Copyright © 2012 John Wiley & Sons, Ltd.