D–A) NFAs have been mainly reported via the 2,9-position connection due to their bisthieno[30,20-b']thienyl[a,h]pyrene fused via a five-membered ring bridge at the ortho-position of pyrene as the representative one named FPIC5, which has prohibited further narrowing their energy gap. Herein, an acceptor FPIC6 was exploited by creating the 1,8-position connection through fusing as bisthieno[30,20-b0]thienyl[f-g,m-n]pyrene linked at the bay-position via a six-membered bridge, with enhanced push–pull characteristics within such A–D–A structure. As a structural isomer of FPIC5, FPIC6 exhibited a much lower bandgap of 1.42 eV (1.63 eV for FPIC5). Therefore, the photocurrent and PCE of PTB7-Th:FPIC6 cells were improved to 21.50 mA cm2 and 11.55%, respectively, due to the balanced mobilities, better photoluminescence quenching efficiency and optimized morphology, which are both
40% better than those of PTB7-Th:FPIC5 cells. Our results clearly proved that a pyrene fused core with 1,8-position connection with electron-withdrawing end groups instead of 2,9-position connection is an efficient molecular design strategy to narrow the optical bandgap and improve the photovoltaic performance of NFA based OSCs.