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The ternary strategy has proven effective in enhancing the performance of organic solar cells (OSCs), yet identifying the optimal third component remains a challenge due to the lack of theoretical frameworks for predicting its impact based on molecular structure. This study addresses this challenge by proposing quantitative parameters derived from molecular surface electrostatic potential (ESP) as criteria for selecting ternary components. The asymmetric acceptor BTP‐OS, which exhibits a lower total average ESP and larger molecular polarization index relative to the host acceptor, is introduced into the PM6:L8‐BO system. This incorporation led to weakened ESP‐induced intermolecular interactions and reduce miscibility with donor polymer, resulting in an optimized multi‐scale morphology of the ternary blend. Consequently, the ternary device achieved an efficiency of 19.72%, one of the highest values for PM6:L8‐BO‐based ternary devices, with enhanced exciton dissociation and charge collection, lower energy disorder, and minimized non‐radiative energy losses. Comparable efficiency improvements are also verified in PM6:BTP‐eC9 and D18:N3 systems, demonstrating the broad applicability of the proposed approach. This study not only provides a practical and effective principle for selecting ternary components but also establishes a broader framework for optimizing ternary OSCs, potentially advancing the development of more efficient OSCs across diverse material systems. [ABSTRACT FROM AUTHOR]