Three donor-acceptor copolymers P1, P2, and P3 with N,N-dodecylpyromellitic diimide as the electron-acceptor unit with three diethynyl-substituted donor monomers: 1,4-diethynyl-2,5-bis(octyloxy)benzene, 2,7-diethynyl-9,9-dioctyl-9H-fluorene, and 3,3-didodecyl-5,5-diethynyl-2,2-bithiophene have been synthesized by Sonogashira crosscoupling polymerization. The synthesized polymers showed deep highest occupied molecular orbital energy levels and larger band gaps (>2.5 eV). Polymers P1, P2, and P3 underwent fluorescence quenching with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), indicating the intermolecular photo-induced charge transfer between the donor polymers and the PCBM acceptor. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1617-1622