Three amorphous piezoelectric polyimides have been synthesized and characterized to analyze their utility for high-temperature applications. The studied polyimides have been prepared from 4,4'-oxydiphthalic anhydride and the diamines 2,4-di(3-aminophenoxy)benzonitrile (poly2-4), 2,6-bis(3-aminophenoxy)benzonitrile (poly2-6), and 1,3-bis-2-cyano-3-(3-aminophenoxy)phenoxybenzene (poly2CN). These polyimides differ in the position of the dipolar groups -CN in the aromatic ring (poly2-4 and poly2-6) and in the number of these groups in the repetitive unit (poly26 and poly2CN). The imidization degree has been studied by Fourier transform infrared (FTIR) and thermogravimetry-mass spectrometry (TG-MS) and thermal properties by differential scanning calorimetry (DSC) and thermogravimetry (TG). The piezoelectric behavior has been analyzed from remnant polarization measurements. (C) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 722-730, 2009