In this study, two D–A polymers consisting of benzodithiophene-4,8-dione and tetrathiophene with or without fluorination were synthesized to reveal the photovoltaic properties of fluorination effect on the polymer backbone. Polymer PDFTB with two fluorine atoms substituted on the backbone exhibits an enhanced π–π stacking effect, deeper HOMO energy level and better backbone planarity than PDTB without fluorine atom substitution. Devices based on PDFTB:ITIC show a power conversion efficiency of 4.39%, which is 15% higher than that of PDTB-based devices due to the higher hole mobility, optimized surface morphology and homogeneous phase separation of the active layer. These results suggest that the fluorination strategy is a facile way to design polymeric donors for solvent-processed polymer solar cells.