A series of triphenylamine-based polymers containing electron-donating methoxy (-OCH3) and electron-withdrawing cyano or nitro (-CN or -NO2) substituents in the main chains have been designed and investigated. These conjugated polymers (P1-P3) could be readily prepared by oxidative coupling polymerization from monomers (M1-M3) using FeCl3 as an oxidant. The P2 and P3 exhibited moderate high T-g values (203-205 degrees C) and thermal stability. These polymers in NMP solution showed UV-vis absorption around 288-404 nm and photoluminescence peaks around 435-492 nm. P1-P3 showed reversible oxidation redox couples at E-onset = 0.67, 0.99, and 1.00 V in solution of 0.1 M tetrabutylammonium perchlorate (TBAP)/acetonitrile (CH3CN), respectively. M3 and P3 exhibited reversible reduction redox couples at E-onset = -1.04 and -1.03 V. These polymers also revealed electrochromic characteristic changing color at different potential. (C) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 285-294, 2009