A series of novel conjugated copolymers of poly[(3-alkylthiophene-2,5-diyl)-alt-(3-cyanothiophene-2,5diyl)] s, (PACTs), containing electron-releasing 3-alkylyl thiophene-2,5-diyl (AT) and electronwithdrawing dibromo 3-cyanothiophene-2, 5-diyl (CT) were synthesized by the polycondensation of a direct heteroarylation reaction. The regular alteration of the electron donor and electron acceptor unit in a polymer backbone led to a decrease in the energy bandgap of conjugated poly(3-alkylylthiophene2,5-diyl) s (P3HT). To accelerate the polycondensation reaction, microwave-assisted heating was used to reduce the reaction time and increase the molecular weight of the polymers. Owing to the strong intermolecular interactions between the neighboring 3-cyanothiophene-2,5-diyl units in the polymer backbone, the lamellar and edge-on structures of the polymer chains were induced on the substrate. The photovoltaic performance of these conjugated copolymers was also evaluated by preparing bulk heterojunction solar cell devices of ITO/PEDOT: PSS/PACT: PC71BM/Al. (C) 2018 Elsevier Ltd. All rights reserved.