In this study, we carefully designed and synthesized three A-D-A type molecules, namely YF-C8-CN, YF-C8-S, and YF-C8-O. These molecules feature a 2,2′-bithiophene core, which bears two 2,4,6-tripropylbenzene steric hindrance groups, as the central electron-donating unit, and utilize rhodanine (Rh), thiazolidinedione, and dicyanoyl-modified benzotriazole (BTA) respectively as the electron acceptor unit (A-unit). We investigated their impact as the third component on the performance of ternary organic solar cells (OSCs). Our studies indicate that YF-C8-S, with rhodanine terminal groups, exhibits complementary absorption characteristics and cascaded energy levels when combined with the host binary system (D18:eC9-4F). Compared to YF-C8-CN and YF-C8-O, ternary OSCs based on YF-C8-S demonstrate significantly higher exciton diffusion and charge transport efficiency, favorably impacting the short-circuit current density (JSC) and fill factor (FF) of the OSCs. Furthermore, devices based on YF-C8-S exhibit reduced non-radiative energy loss, contributing to an enhanced open-circuit voltage (VOC). Consequently, ternary OSCs based on YF-C8-S achieve a remarkable efficiency of 19.12%, positioning it among the highest reported values. This comprehensive research on the third component of the YF-C8 series underscores their significant potential for fabricating high-performance ternary OSCs.