The trade‐off between the open‐circuit voltage (Voc) and short‐circuit current density (Jsc) has become the core of current organic photovoltaic research, and realizing the minimum energy offsets that can guarantee effective charge generation is strongly desired for high‐performance systems. Herein, a high‐performance ternary solar cell with a power conversion efficiency of over 18% using a large‐bandgap polymer donor, PM6, and a small‐bandgap alloy acceptor containing two structurally similar nonfullerene acceptors (Y6 and AQx‐3) is reported. This system can take full advantage of solar irradiation and forms a favorable morphology. By varying the ratio of the two acceptors, delicate regulation of the energy levels of the alloy acceptor is achieved, thereby affecting the charge dynamics in the devices. The optimal ternary device exhibits more efficient hole transfer and exciton separation than the PM6:AQx‐3‐based system and reduced energy loss compared with the PM6:Y6‐based system, contributing to better performance. Such a “two‐in‐one” alloy strategy, which synergizes two highly compatible acceptors, provides a promising path for boosting the photovoltaic performance of devices.

Manipulating charge generation in a broad spectral region has proved to be crucial for nonfullerene‐electron‐acceptor‐based organic solar cells (OSCs). 16.64% high efficiency binary OSCs are achieved through the use of a novel electron acceptor AQx‐2 with quinoxaline‐containing fused core and PBDB‐TF as donor. The significant increase in photovoltaic performance of AQx‐2 based devices is obtained merely by a subtle tailoring in molecular structure of its analogue AQx‐1. Combining the detailed morphology and transient absorption spectroscopy analyses, a good structure–morphology–property relationship is established. The stronger π–π interaction results in efficient electron hopping and balanced electron and hole mobilities attributed to good charge transport. Moreover, the reduced phase separation morphology of AQx‐2‐based bulk heterojunction blend boosts hole transfer and suppresses geminate recombination. Such success in molecule design and precise morphology optimization may lead to next‐generation high‐performance OSCs.