In this study, the new polymer-silica hybrid materials were prepared based on the organo-soluble polyimides of 4,4'-hexafluoroisopropylidenediphthalic anhydride (6FDA) and four diamines. 3-Aminopropyl trimethoxysilane (APrTEOS) and gamma-glycidyloxypropyltrimethoxysilanes (GOTMS) were used to increase the intrachain chemical bonding and interchain hydrogen bonding between the polyimide and silica moieties, respectively. The chemical interaction would significantly affect the morphologies and properties of the prepared films. Highly homogeneous hybrid thin films were obtained according to the studies of atomic force microscopy and TEM. The silica size observed by the TEM picture was smaller than 5 nm. The thermal properties of the organo-soluble polyimides were significantly enhanced by hybridizing only 6.30-7.99 wt% of silica. The intrachain chemical bonding could effectively enhance the coefficient of thermal expansion in comparison with the interchain interaction. Low dielectric constants in the range of 2.85-3.73 were obtained for the prepared hybrid films. The refractive indices of the prepared materials could be tuned through the polyimide structure or the silica content. The optical losses of the planar waveguides based on the prepared polyimides and their hybrids at 1310 nm were in the range of 0.5-2.7 dB/cm, which were mostly due to the higher harmonics of the aromatic C-H vibration and the extrinsic loss. The prepared polyimide-silica hybrid materials could have potential applications for microelectronics or optical communications. (C) 2003 Elsevier Ltd. All rights reserved.