Symmetric conjugated molecules can be broken through suitable synthetic strategies to construct novel asymmetric molecules, which can largely broaden the material library. In the field of organic solar cells, fused‐ring electron acceptors (FREAs) with the A‐DA'D‐A type backbone structure have attracted much attention and enabled power conversion efficiencies (PCE) exceeding 18%. Among them, Y6 is one of the most classic FREAs that can derive many symmetric and asymmetric molecules and exhibit unique optoelectronic properties. Thus, in this review, the focus is on the recent progress of Y6‐derived asymmetric FREAs containing a dipyrrolobenzothiadiazole segment, which can be classified as the following three categories: asymmetric end group, asymmetric central core and asymmetric side chain. The relationship of the molecular structure, optoelectronic properties, and device performance is discussed in detail. Finally, the future design directions and challenges faced by this kind of photovoltaic materials are given.

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The side-chain engineering of A-DA'D-A-type nonfullerene acceptors (NFAs), well-known as Y6 series, is an efficient approach for retaining the physical properties of Y6-series but allowing manipulation of the solubility, crystallization,...

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