Efficient organic photovoltaic cells (OPVs) are fabricated using two structurally similar Y6 derivations (BTP‐BO‐4F and Y6‐1O) as acceptor and PM6 as donor. The two binary OPVs exhibit a high fill factor (FF) (>76%), the complementary short‐circuit‐current density ( J SC ) and open‐circuit voltage ( V OC ). The high FFs of binary OPVs indicate the good compatibility of corresponding materials to form efficient charge transport channels. A power conversion efficiency (PCE) of 17.59% is obtained from ternary OPVs with 15 wt% Y6‐1O in acceptors, benefiting from the simultaneously improved J SC of 26.13 mA cm −2 , a V OC of 0.860 V, and an FF of 78.26%. The values of V OC of ternary OPVs can be gradually increased along with the incorporation of Y6‐1O, suggesting the preferred formation of an alloyed state between BTP‐BO‐4F and Y6‐1O due to their good compatibility. Meanwhile, the cascaded energy levels of BTP‐BO‐4F and Y6‐1O can form efficient electron transport channels in ternary active layers. The main contribution of Y6‐1O can be summarized as enhancing photon harvesting, optimizing phase separation, and adjusting molecular arrangement. The experimental results may provide new insight on developing efficient ternary OPVs by selecting two well‐compatible acceptors.