The power conversion efficiencies (PCEs) of small molecule acceptor (SMA)‐based organic solar cells have already exceeded 18%. However, the development of polymer acceptors still lags far behind their SMA counterparts mainly due to the lack of efficient polymer acceptors. Herein, a series of polymer acceptors named PY‐X (with X being the branched alkyl chain) are designed and synthesized by employing the same central core with the SMA L8‐BO but with different branched alkyl chains on the pyrrole motif. It is found that the molecular packing of SMA‐HD featuring 2‐hexyldecyl side chain used in the synthesis of PY‐HD is similar to L8‐BO, in which the branched alkyl chains lead to condensed and high‐order molecular assembly in SMA‐HD molecules. When combined with PM6, PY‐HD‐based all polymer solar cell (all‐PSC) exhibits a high PCE of 16.41%, representing the highest efficiency for the binary all‐PSCs. Moreover, the side‐chain modification on the pyrrole site position further improves the performance of the all‐PSCs, and the PY‐DT‐based device delivers a new record high efficiency of 16.76% (certified as 16.3%). The work provides new insights for understanding the structure–property relationship of polymer acceptors and paves a feasible avenue to develop efficient conjugated polymer acceptors.

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