A new class of donor–acceptor-containing oligothienylenevinylenes with a triphenylamine donor and a dicyanovinyl group as acceptor has been synthesized and characterized. By extending the oligothiophene backbone, both the optical bandgaps and the charge-transport properties can be tuned. These oligothienylenevinylene derivatives show intense charge-transfer absorption bands that cover the entire visible spectrum, with low optical bandgaps of approximately 1.64 eV. In addition, electrochemical studies reveal that these compounds possess relatively large ionization potentials of approximately 5.5 eV. On the basis of these newly developed dicyanovinyl-substituted chromophores as donor materials and C60 as acceptor material, bilayer organic photovoltaic devices have been fabricated, with the best device showing a high power conversion efficiency (PCE) of 2.0 %, with an open-circuit voltage of 0.68 V and a fill factor of 0.60 after thermal annealing. The obvious morphology change with the formation of small domains in thin films and the reduction of series resistance are believed to be responsible for the dramatic performance improvement upon thermal annealing.