Two copolymers having D-A-D-A (P1) and D-A (P2) structures with quinoxaline acceptor unit and dithienosilole donor unit were synthesized and their optical and electrochemical (both experimental and theoretical) properties were investigated. The optical properties showed that these copolymers P1 and P2 exhibit optical bandgaps of 1.54 and 1.62 eV, respectively, with broader absorption profiles extending up to 800 nm and 770 nm, respectively. The electrochemical investigation of these two copolymers indicates that they exhibit suitable highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels for efficient exciton dissociation and high open circuit voltage in the resultant polymer solar cells (PSCs). These copolymers were used as donors along with the PC71BM as acceptor for the fabrication of solution processed bulk heterojunction PSCs. The optimized P1:PC71BM and P2:PC71BM active layers treated with solvent vapor treatment showed overall power conversion efficiency (PCE) of 7.16% and 6.57%, respectively. The higher PCE of P1-based device as compared to P2 might be attributed to higher crystallinity of P1 and good hole mobility resulting more balanced charge transport. (c) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 376-386