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Herein, we develop four trimeric GMAs (named 3Y\u2010site, including wing\u2010sites\u2010linked 3Y\u2010Wing, end\u2010sites\u2010linked 3Y\u2010End, hybrid wing\/end\u2010sites\u2010linked 3Y\u2010EWE and 3Y\u2010WEW) with the same alkylated linker but different linking sites to fine\u2010tune molecular optoelectronic properties. Among them, 3Y\u2010Wing with a superior planarity and extensibility possesses broadened absorption, better crystallinity, superior packing, and higher glass transition temperature, resulting in an optimized phase separation. The optimized devices with binary PM6:3Y\u2010Wing and ternary PM6:L8\u2010BO:3Y\u2010Wing achieve both champion PCEs of 15.0% and 19.1%, respectively, along with enhanced light, thermal, and storage stabilities, outperforming devices based on all other 3Y\u2010site counterparts. In the classic D18:L8\u2010BO host system, the effectiveness of 3Y\u2010Wing in boosting PCE is further validated, and the resulted ternary devices deliver an excellent PCE of 20.23%, setting an efficiency record among the reported trimeric GMAs. Moreover, the 3Y\u2010Wing based OSCs offer a better balance of high PCE and stability, further distinguishing them within 3Y\u2010site series. Our developed wing\u2010sites\u2010linked trimeric 3Y\u2010Wing is a promising candidate to achieve both high device efficiency and stability.<\/jats:p>","DOI":"10.1002\/anie.6120368","type":"journal-article","created":{"date-parts":[[2026,2,6]],"date-time":"2026-02-06T09:22:08Z","timestamp":1770369728000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Trimeric Acceptors with Fine\u2010Tuned Alkyl\u2010Linkage Sites for 20.23% Efficiency and Stable Organic Solar Cells"],"prefix":"10.1002","volume":"65","author":[{"given":"Tengfei","family":"Li","sequence":"first","affiliation":[{"name":"State Key Laboratory For Mechanical Behavior of Materials Xi'an Jiaotong University  Xi'an China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wenjing","family":"Zhou","sequence":"additional","affiliation":[{"name":"College of Chemistry Key Lab of Environment\u2010Friendly Chemistry and Application (Ministry of 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