In this study, we designed and synthesized two NFREAs, 2BTh-3F and 2BTh-CN, incorporating distinct substituents to modulate their electron-withdrawing properties. We meticulously explore the distinct impacts of these substituents on NFREA performance. Our investigation revealed that the introduction of 3,5-difluoro-4-cyanophenyl in 2BTh-CN significantly enhanced electron withdrawal and intramolecular charge transfer, leading to a red-shifted absorption spectrum and optimized energy levels. Consequently, organic solar cells (OSCs) utilizing 2BTh-CN demonstrate a notable power conversion efficiency (PCE) of 15.07%, outperforming those employing 2BTh-3F (PCE of 9.34%). Moreover, by incorporating 2BTh-CN into the D18:2BTh-C2 system as a third component, we achieve a PCE exceeding 17% in a high-performing ternary OSC, ranking among the most efficient NFREA-based OSCs reported to date. Overall, our study underscores the potential of deliberate design and optimization of non-fused ring acceptor molecular structures to attain outstanding photovoltaic performance.