π-Bridges play a crucially important role in determining the optical absorption, bandgap and energy levels of donor-π-acceptor-π type conjugated polymers. In this contribution, a new polymer donor named PBT1-C-2Cl is synthesized by inserting the chlorine atoms onto π-bridges of the polymer PBT1-C. The introduction of chlorine atoms enables PBT1-C-2Cl with a lower highest occupied molecular orbital energy level and enhanced crystallinity than those of PBT1-C due to the high electronegativity and big atomic radius of chloride atom. When PBT1-C-2Cl is blended with the non-fullerene acceptor IT-4F, a high power conversion efficiency (PCE) of 12.7%, an open-circuit voltage (V_oc) of 0.85 V and an impressive fill factor (FF) of 76.0% are achieved, which are all higher than those of PBT1-C:IT-4F based devices (PCE = 10.9%, V_oc = 0.79 V and FF = 70.5%). The enhanced charge dissociation, efficient charge transport and reduced charge recombination account for the improved photovoltaic performance of PBT1-C-2Cl: IT-4F devices. The results indicate that inserting chlorine atoms onto π-bridges is a rational strategy for the synthesis of high-performance donor-π-acceptor-π type conjugated polymer donors.