Four alkyl-substituted thiophene-3-carboxylate containing donor-acceptor (D-A) copolymers were designed, synthesized, and characterized. Thiophene-3-carboxylate was used as a weak electron acceptor unit in the copolymers to provide a deeper highest occupied molecular orbital (HOMO) level for obtaining a higher open-circuit voltage in polymer solar cells (PSCs). The resulting bulk heterojunction PSCs, made of the copolymers and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM), exhibited different short circuit currents (J(SC)s) and open-circuit voltages (V(OC)s), depending on the length of alkyl side-chain in the thiophene-3-carboxylate unit. Among all fabricated photovoltaic (PV) devices, PC2:PC71BM (1:1 wt. ratio) showed the highest efficiency with the highest Jsc of 10.5 mA/cm(2). Although PC5:PC71BM (1:1) displayed the highest V-OC of 0.93 V. the device efficiency was observed to be poor, which is due to poor nanophase segregation. This comparison shows that the side-chain of thiophene carboxylate in these copolymers plays a very important role in the device efficiency. (C) 2012 Elsevier Ltd. All rights reserved.