A novel adamantoxytriphenylamine-containing diamine monomer, 4-(1-adamantoxy)-4',4"-diaminotriphenylamine, was synthesized from readily available reagents. Two series of novel electroactive aromatic polyamides and polyimides with bulky 4-(1-adamantoxy)triphenylamine moieties were prepared from the newly synthesized diamine monomer with various aromatic dicarboxylic acids and tetracarboxylic dianhydrides, respectively. All the resulting polyamides and most of the polyimides were readily soluble in polar organic solvents and could be solution cast into tough and flexible films. These polymers showed moderate to high glass transition temperatures in the range of 263-311 degrees C, and they were fairly stable up to a temperature above 480 degrees C (for polyamides) or 500 degrees C (for polyimides). Cyclic voltammograms of the polyamides and polyimides showed one pair of reversible redox waves with oxidation half-wave potentials (E-1/2) in the range of 0.78-0.81 and 0.97-1.05 V, respectively, versus Ag/AgCl in an acetonitrile solution. In addition, the polymers were found to display stable electrochromic properties by repeated cyclic scans between 0.0 and 1.1-1.2 V, with coloration change from a colorless or pale yellowish neutral form to a dark blue or bluish green oxidized form. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1740-1755, 2009