Here, a pair of A1 -D-A2 -D-A1 unfused ring core-based nonfullerene small molecule acceptors (NF-SMAs), BO2FIDT-4Cl and BT2FIDT-4Cl is synthesized, which possess the same terminals (A1 ) and indacenodithiophene unit (D), coupling with different fluorinated electron-deficient central unit (difluorobenzoxadiazole or difluorobenzothiadiazole) (A2 ). BT2FIDT-4Cl exhibits a slightly smaller optical bandgap of 1.56 eV, upshifted highest occupied molecular orbital energy levels, much higher electron mobility, and slightly enhanced molecular packing order in neat thin films than that of BO2FIDT-4Cl. The polymer solar cells (PSCs) based on BT2FIDT-4Cl:PM7 yield the best power conversion efficiency (PCE) of 12.5% with a Voc of 0.97 V, which is higher than that of BO2FIDT-4Cl-based devices (PCE of 10.4%). The results demonstrate that the subtle modification of A2 unit would result in lower trap-assisted recombination, more favorable morphology features, and more balanced electron and hole mobility in the PM7:BT2FIDT-4Cl blend films. It is worth mentioning that the PCE of 12.5% is the highest value in nonfused ring NF-SMA-based binary PSCs with high Voc over 0.90 V. These results suggest that appropriate modulation of the quinoid electron-deficient central unit is an effective approach to construct highly efficient unfused ring NF-SMAs to boost PCE and Voc simultaneously.