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However, previous work mainly focused on the aspects of donors, but how the polymer acceptor influences its morphology and device performances is lacking in study. In this work, we apply three polymerized nonfullerene small molecules as acceptors, combining film\u2010forming kinetics and microstructure characterization to investigate the efficient S<jats:sub>D<\/jats:sub>\/P<jats:sub>A<\/jats:sub>\u2010type OSCs requirements on polymers. We found the following two results: Strong miscibility between donor and acceptor would facilitate the acceptor inducing the donor to adopt a face\u2010on packing; under similar miscibility, the inferior crystallinity of the acceptor facilitates a more proper phase separation. Hence, the DTBDT\u2010C3\u2010D6:PY2S\u2010F\u2010based S<jats:sub>D<\/jats:sub>\/P<jats:sub>A<\/jats:sub>\u2010type OSCs with the best miscibility achieve an impressive PCE of 13.65% with both high short\u2010circuit current density (<jats:italic>J<\/jats:italic>sc) of 20.73\u00a0mA cm<jats:sup>\u22122<\/jats:sup> and fill factor (FF) of 72.93%, which are among the highest values in the reported binary S<jats:sub>D<\/jats:sub>\/P<jats:sub>A<\/jats:sub>\u2010type OSCs so far. Our work provides a new perspective for the development of highly efficient S<jats:sub>D<\/jats:sub>\/P<jats:sub>A<\/jats:sub>\u2010type OSCs with polymer acceptor matched to small molecule donor.<\/jats:p>","DOI":"10.1002\/chem.202501583","type":"journal-article","created":{"date-parts":[[2025,6,4]],"date-time":"2025-06-04T23:30:22Z","timestamp":1749079822000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Small Molecule Donor\/Polymer Acceptor Organic Solar Cells with Efficiency of 13.65% Enabled by Film Formation Kinetics and Phase Separation Control"],"prefix":"10.1002","volume":"31","author":[{"given":"Mengying","family":"Wu","sequence":"first","affiliation":[{"name":"College of Chemistry Zhengzhou University  Zhengzhou 450001 China"},{"name":"Key Laboratory of Nanosystem and Hierarchical Fabrication of Chinese Academy of Sciences National Center for Nanoscience and Technology  Beijing 100190 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ruimin","family":"Zhou","sequence":"additional","affiliation":[{"name":"College of Chemistry Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hui","family":"Wang","sequence":"additional","affiliation":[{"name":"College of Chemistry Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Caixuan","family":"Wang","sequence":"additional","affiliation":[{"name":"Key Laboratory of Nanosystem and Hierarchical Fabrication of Chinese Academy of Sciences National Center for Nanoscience and Technology  Beijing 100190 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hao","family":"Zhang","sequence":"additional","affiliation":[{"name":"Key Laboratory of Nanosystem and Hierarchical Fabrication of Chinese Academy of Sciences National Center for Nanoscience and Technology  Beijing 100190 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dingding","family":"Qiu","sequence":"additional","affiliation":[{"name":"Key Laboratory of Nanosystem and Hierarchical Fabrication of Chinese Academy of Sciences National Center for Nanoscience and Technology  Beijing 100190 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Huijuan","family":"Bi","sequence":"additional","affiliation":[{"name":"Key Laboratory of Nanosystem and Hierarchical Fabrication of Chinese Academy of Sciences National Center for Nanoscience and Technology  Beijing 100190 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuhan","family":"Wang","sequence":"additional","affiliation":[{"name":"Key Laboratory of Nanosystem and Hierarchical Fabrication of Chinese Academy of Sciences National Center for Nanoscience and Technology  Beijing 100190 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jianqi","family":"Zhang","sequence":"additional","affiliation":[{"name":"Key Laboratory of Nanosystem and Hierarchical Fabrication of Chinese Academy of Sciences National Center for Nanoscience and Technology  Beijing 100190 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dan","family":"Deng","sequence":"additional","affiliation":[{"name":"Key Laboratory of Nanosystem and Hierarchical Fabrication of Chinese Academy of Sciences National Center for Nanoscience and Technology  Beijing 100190 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yanlin","family":"Song","sequence":"additional","affiliation":[{"name":"Key Laboratory of Green Printing Institute of Chemistry Chinese Academy of Sciences (ICCAS) National Laboratory for Molecular Sciences (BNLMS)  Beijing 100190 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhixiang","family":"Wei","sequence":"additional","affiliation":[{"name":"Key Laboratory of Nanosystem and Hierarchical Fabrication of Chinese Academy of Sciences National Center for Nanoscience and Technology  Beijing 100190 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,6,19]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1038\/nphoton.2012.11"},{"key":"e_1_2_8_2_1","first-page":"4","author":"Servaites J. 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