Poly(amide-imide), PI, hybrid films are prepared by using sol-gel techniques. First, the poly(amide amic acid) with controlled block chain length of 5000 and 10,000 g/mol and uncontrolled chain length are synthesized by condensation reaction with 4,4-diaminodiphenyl ether (ODA), 3,3,4,4-benzophenonetetracarboxylic dianhydride (BTDA), trimellitic anhydride chloride (TMAC) and terminated with p-aminopropyltrimethoxysilane (APrTMOS). And then the imidization reactions of poly (amide amic acid) are proceeded to obtain the poly (amide-imide) hybrid film. Hybrid films with 5000 g/mol block chain length possess higher storage modulus, lower glass transition temperature and damping intensity comparing to films with 10,000 g/mol block chain length. The addition of TMAC to the poly(amide-in-tide) hybrids is due to the increase of toughness and intermolecular hydrogen bonding, which is the average strength of intermolecular bonding and studied by the hydrogen-bonded fraction (F-bonded), frequency difference (Delta v) and shiftment. Meanwhile, PI hybrid films containing more APrTMOS and TMAC content possess higher thermal and mechanical properties. On the other hand, hybrid films with 10,000 g/mol block chain length and more TMAC content have higher gas permeabilities than other films. The degradation temperatures of 5 wt %, loss of all hybrid films are all higher than 540 degrees C and increased as the increase of TMAC content. (c) 2007 Wiley Periodicals, Inc.