An alternating polymer (PFOFTQx) with 9,9-dioctylfluorene (FO) as electron-rich unit and fluorine substituted quinoxaline (FTQx) as electron-withdrawing unit was synthesized and characterized. PFOFTQx showed similar absorption property with that of the counterpart polymer without fluorine atom (synthesized APFO-15). However, the low-lying highest occupied molecular orbit (HOMO) energy level of PFOFTQx was -5.37 eV, about 0.07 eV smaller than that of synthesized APFO-15. In order to study the photovoltaic properties of the materials, polymer solar cells (PSCs) were fabricated with PFOFTQx as donor blended with [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) as acceptor. The power conversion efficiency (PCE) of PSC was 1.77% with a high open-circuit voltage (V-oc) of 0.90 V for an optimized PFOFTQx:PC61BM weight ratio of 1:5, in comparison with that of synthesized APFO-15-based device (PCE of 1.60% with V-oc of 0.77 V). This study indicated that fluorine substituted quinoxaline-based polymers would be promising material with a higher V-oc for the application in polymer solar cells. (C) 2013 Elsevier Ltd. All rights reserved.