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Herein, we expand the functional scope of CPPs by covalently integrating a carbon\u2010nanohoop scaffold with Y\u2010series electron acceptors to develop a novel 3D trimeric acceptor, CPP\u20103Y. Distinct from conventional planar molecules, CPP\u20103Y combines radially oriented \u03c0\u2010conjugation, a continuously curved \u03c0\u2010surface, and sterically hindered 3D topology, resulting in strong aggregation with low crystallinity. When introduced as a third component into the D18:L8\u2010BO\u2010X binary system, CPP\u20103Y preferentially associates with the L8\u2010BO\u2010X\u2010rich acceptor phase, resulting in large fibrillar structures in blended thin films. This narrows the energetic tail\u2010state distribution, suppresses trap\u2010assisted and non\u2010radiative recombination, and enables more balanced charge transport. Consequently, D18:L8\u2010BO\u2010X:CPP\u20103Y ternary OSCs achieve a PCE of 20.62%, outperforming binary devices (19.90%). They also retain over 80% of their initial efficiency after 964\u00a0h at 70\u00a0\u00a0\u00b0C, whereas the binary devices fall below this level after 432\u00a0h. This work demonstrates that cyclic electron acceptors with 3D configurations and strong aggregation can act as morphological regulators to tune the phase separation of photoactive layers and hence realize high PCEs in OSCs.<\/jats:p>","DOI":"10.1002\/anie.8288920","type":"journal-article","created":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T08:42:40Z","timestamp":1790671360000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["A 3D Cycloparaphenylene\u2010Cored Trimeric Electron Acceptor Regulates Acceptor Fibril Morphology for 20.6%\u2010Efficient Ternary Organic Solar Cells"],"prefix":"10.1002","author":[{"given":"Bo","family":"Wang","sequence":"first","affiliation":[{"name":"Beijing Advanced Innovation Center for Soft Matter Science and Engineering &amp; State Key Laboratory of Organic\u2010Inorganic Composites Beijing University of Chemical Technology  Beijing P. R. 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