Narrow bandgap n‐type organic semiconductors (n‐OS) have attracted great attention in recent years as acceptors in organic solar cells (OSCs), due to their easily tuned absorption and electronic energy levels in comparison with fullerene acceptors. Herein, a new n‐OS acceptor, Y5, with an electron‐deficient‐core‐based fused structure is designed and synthesized, which exhibits a strong absorption in the 600–900 nm region with an extinction coefficient of 1.24 × 105 cm−1, and an electron mobility of 2.11 × 10−4 cm2 V−1 s−1. By blending Y5 with three types of common medium‐bandgap polymers (J61, PBDB‐T, and TTFQx‐T1) as donors, all devices exhibit high short‐circuit current densities over 20 mA cm−2. As a result, the power conversion efficiency of the Y5‐based OSCs with J61, TTFQx‐T1, and PBDB‐T reaches 11.0%, 13.1%, and 14.1%, respectively. This indicates that Y5 is a universal and highly efficient n‐OS acceptor for applications in organic solar cells.

Ternary solar cells with an efficiency of 16.7% were enabled through the use of PCBM as a higher LUMO-level acceptor additive to concurrently increase Voc, Jsc and FF values.

The short circuit current density and fill factor are improved in ternary organic solar cell due to the high morphology compatibility.

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