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Fullerene‐free OSCs employing n‐type small molecules or polymers as the acceptors have recently experienced a rapid rise with efficiencies exceeding 12%. Owing to the good optoelectronic and morphological tunabilities, non‐fullerene acceptors exhibit great potential for realizing high‐performance and practical OSCs. In this Review, recent exciting progress made in developing highly efficient non‐fullerene acceptors is summarized, mainly correlating factors like absorption, energy loss and morphology of new materials to their correspondent photovoltaic performance.