Two polythiophenes with carboxylate side chains and vinylene linkers in conjugated backbones, i.e., poly [5,5'-(E)-bis(2-hexyldecyl)-2,2'-(ethene-1,2-diyl) bis(thiophene-3-carboxylate)-alt-5,5'-2,2'-bithio-phene] (PBT) and poly[5,5'-(E)-bis(2-hexyldecyl)-2,2'-(ethene-1,2-diyl) bis(thiophene-3-carboxylate)alt-5,5'-thieno[3,2-b] thiophene] (PTT), were synthesized and characterized. Compared to poly(3-hexylthiophene) (P3HT), both polymers displayed deeper HOMO energy levels caused by the introduction of the electron-withdrawing carboxylate group and lower band gaps and shorter pi-pi stacking distances (ca. 3.5 angstrom) due to the incorporation of vinylene linkers in the conjugated backbones. Polymer PBT possesses greater self-organization ability and thereby more ordered intermolecular packing in solid state. Consequently, organic field-effect transistors (OFETs) based on PBT showed a hole mobility of 0.24 cm(2) V(-1)s(-1), much higher than that (0.073 cm(2) V(-1)s(-1)) of PTT. Polymer solar cells (PSCs) with the two polymers as donor materials and [6,6]-phenyl-C-71-butyric acid methyl ester (PC71BM) as acceptor material were fabricated, and both PBT-and PTT-based PSCs showed open circuit voltage (V-oc) above 0.8 V. Owing to the better hole transport property and more ordered nano-fibrillar film morphology, PBT-based PSCs exhibited a superior photovoltaic performance with power conversion efficiency (PCE) of 6.25%, higher than that of PTT-based PSCs (PCE = 5.53%). This study indicates that simultaneously introducing electron-withdrawing carboxylate in side chains and vinylene linkers in conjugated backbones could efficiently tune the energy levels and enhance the pi-pi interactions between conjugated backbones. (C) 2018 Elsevier Ltd. All rights reserved.