摘要： Non-radiative recombination energy loss (ΔE3) plays a key role in enhancing device efficiencies for polymer solar cells (PSCs). Up to now, there is no clear resolution for reducing ΔE3 via molecular design. Herein, we report two conjugated polymers, PBDB-P-p and PBDB-P-m, which are integrated from benzo[1,2-b:4,5-b′]dithiophene (BDT) with alkylthio chain substituted at para- or meta- position on pendent benzene and benzo[1,2-c:4,5-c′]dithiophene-4,8-dione (BDD). Two polymers have different temperature-dependent aggregation properties, but similar molecular energy levels. When BO-4Cl was used as acceptor to fabricate PSCs, the device of PBDB-P-p:BO-4Cl displayed a maximal power conversion efficiency (PCE) of 13.83%, while the best device of PBDB-P-m:BO-4Cl exhibited a higher PCE of 14.12%. The close JSCs and FFs in both PSCs are attributed to their formation of effective nanoscale phase-separation as confirmed by atomic force microscopy (AFM) measurements. We find that the PBDB-P-m-based device has one order of magnitude higher of electroluminescence quantum efficiency (EQEEL) than that in PBDB-P-p-based one, which could arise from the relatively weak aggregation in PBDB-P-m-based film. Thus, the PBDB-P-m-based device has a remarkably enhanced VOC of 0.86 V in contrast to 0.80 V in PBDB-P-p-based device. This study offers a feasible structural optimization way on the alkylthio side chain substitute position on the conjugated polymer to enhance VOC by reducing non-radiative recombination energy loss in resulting PSCs.