The alkyne moieties of poly(3-hexylthienyleneethynylene) were reacted with tetracyanoethylene or 7,7,8,8-tetracyano-quinodimethane by microwave irradiation to produce donor-acceptor chromophores in the polymer main chain. The resulting polymers were fully characterized by GPC, H-1 NMR, and IR spectroscopies, and elemental analyses. They were both thermally and chemically stable, as revealed by thermogravimetric analyses and ESR measurements. UV-vis-NIR spectroscopy revealed charge-transfer bands in the low-energy region, and electrochemistry confirmed the narrower band gaps with the elevated HOMO and lower LUMO levels relative to the precursor polymer. To take advantage of these postfunctionalization methods, p-type doping of the polymers with 12 was attempted. Room temperature conductivities of the postfunctionalized polymers reached 4.5 x 10(-5) S cm(-1), which was about 10 times greater than that of the precursor polymer. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 1013-1020, 2011