We report the effect of organosilica precursor isomers on the interfacial interaction between polyimide and organosilica in polyimide/organosilica hybrid composite films. Poly(4,4 '-oxydianiline biphenyltetracarboxamic acid) (BPDA-ODA PAA) was used as the polyimide precursor, while the organosilica was made using o-substituted, m-substituted, and p-substituted phenyl organosilica precursor isomers. For the preparation of precursor hybrid films, BPDA-ODA PAA and organosilica precursors were mixed and then the organosilica precursors were converted to corresponding organosilica via sol-gel process. Finally, these precursor films were converted to corresponding polyimide/organosilica hybrid films by the thermal imidization of BPDA-ODA PAA, which results in poly(4,4-oxydianiline biphenyltetracarboximide) (BPDA-ODA PI). The polyimide/organosilica hybrid films were characterized using three distinctive nuclear magnetic resonance spectroscopies (H-1 NMR, C-13-CPMAS-NMR, and Si-29-MAS-NMR), wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS), and peel strength measurement. We found that the m-substituted phenyl organosilica shows poorer interfacial interaction with BPDA-ODA PI than do the o- or p-substituted phenyl organosilicas. It was observed, however, that the peel strength of the hybrid films against an aluminum substrate increased with increasing contents of organosilicas, regardless of the nature of the organosilica isomers. (c) 2006 Wiley Periodicals, Inc.