A novel route to synthesize polyimide (PI)/silica hybrid films with improved thermal and mechanical properties was developed. Low-molecular-weight poly(amic acid) (PAA), which is the precursor of PI, was successfully synthesized by controlling the molar ratio of monomers, [4,4'-(4,4'-isopropylidenediphenoxy) bis(phthalic anhydride)] (IDPA) and 2,2'-bis(4-(4-aminophenoxy)phenyl)propane (BAPP). The PM with its low-molecule-weight feature showed good compatibility with silica-sol and dispersed well within the network of silica-sol. Silica nanoparticles with an average size of 20 nm were obtained without adding coupling agents and dispersed homogenously within the resulting PI/silica hybrid films due to the hydrogen bonding between Si-OH groups and C=O in imide rings of polyimide. The improvement in the storage modulus and the coefficient of thermal expansion (CTE) by hybrid films was revealed. With the presence of 50 wt.% silica in hybrid films, the storage modulus was 5857 MPa and the CTE was 18.1 ppm/degrees C. compared with 1620 MPa and 76.5 ppm/degrees C for pure PI. Most importantly, the transmission at 550 nm was 81.4% for the hybrid film with 50 wt.% silica, which is close to 87.5% for pure PI. The CTE of the hybrid film dropped to the level comparable with that of copper without sacrificing its transparency, which was associated with the well-dispersed silica nanoparticles and the semi-interpenetrating polymer network (semi-IPN) structure within the PI matrix. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.