We report here electrochemical synthesis of novel soluble donor-acceptor (D-A) polymer with suitably functionalized perylenetetracarboxylic diimide dye derivative covalently linked to carbazole moiety (Cbz-PDI). The band gap, E, was measured using UV-Vis spectroscopy and compared with that obtained by cyclic voltammetry (CV). Efficient intramolecular electron transfer from carbazole-donor to perynediimide-acceptor leads to remarkable fluorescence quenching of the perylene core. Furthermore, spectroelectrochemical property and surface morphology of the polymer film were investigated. Characteristic monoanion and dianion radical bands on the UV-Vis absorption spectra attributed to the electrochemical reduction of the neutral polymer were observed. During the reduction process, red color of the film turned into blue and violet, respectively. Finally, the photovoltaic performance of the D-A double-cable polymer was checked and nearly 0.1% electrical conversion efficiency is obtained under simulated AM 1.5 solar light with 100 mW/cm(2) radiation power. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6280-6291, 2009