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To address this, two small\u2010molecule donors, C1 and C2, were designed with identical backbones but distinct aromatic connecting units: a phenyl linkage in C1 and a thiophene linkage in C2. It is revealed that steric torsion is utilized by the phenyl linkage in C1 to suppress excessive self\u2010aggregation and induce balanced, mixed\u2010orientation molecular packing. In contrast, the thiophene linkage in C2 promotes a coplanar backbone with tighter, predominantly face\u2010on \u03c0\u2013\u03c0 stacking, leading to over\u2010crystallization. Consequently, C1 facilitates finer interpenetrating networks with redistributed \u03c0\u2013\u03c0 interactions, supporting efficient in\u2010plane charge transport. Benefiting from this optimized morphology and favorable energy alignment, the PM6:Y6:C1 device achieves an outstanding Fill Factor (FF) of 77.90% and a Power Conversion Efficiency (PCE) of 17.98%, significantly outperforming binary devices and the C2\u2010based ternary devices. This work establishes aromatic connecting unit modulation as a pivotal strategy for precisely controlling aggregation and nanoscale morphology in high\u2010performance TOSCs.<\/jats:p>","DOI":"10.1002\/smll.74103","type":"journal-article","created":{"date-parts":[[2026,6,5]],"date-time":"2026-06-05T11:18:34Z","timestamp":1780658314000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Aromatic Connectivity Governs Aggregation and Morphology in Ternary Organic Solar Cells"],"prefix":"10.1002","volume":"22","author":[{"given":"Jing","family":"Lv","sequence":"first","affiliation":[{"name":"School of Materials Science and Engineering Ocean University of China  Qingdao China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guoqing","family":"Lin","sequence":"additional","affiliation":[{"name":"School of Materials Science and Engineering Ocean University of China  Qingdao 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