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However, forming such fibrous morphology is difficult to control in polymer:non\u2010fullerene acceptor (NFA) systems, mainly because of the relatively weak intermolecular interactions between components and fast film formation dynamics. Herein, we propose a co\u2010solvent combined with solid additive strategy to synchronously regulate film formation kinetics and tune the intermolecular interaction in D18:L8\u2010BO systems. The high\u2010boiling\u2010point co\u2010solvent, trichloroethylene (TCE) slows evaporation and promotes uniform aggregation, while the high\u2010melting\u2010point solid additive, 5,6\u2010dibromo\u20102,1,3\u2010benzothiadiazole (BBT) enhances intermolecular interactions and prolongs crystallization. In situ characterizations reveal that both the liquid\u2010phase stage and liquid\u2010to\u2010solid transition stage of D18 and L8\u2010BO in the blend are prolonged effectively. As a result, an optimized fibrous network with a wider fiber diameter (10.94\u00a0nm) is formed. The enlarged coherence lengths of D18:L8\u2010BO in both out\u2010of\u2010plane (010) and (100) directions indicate enhanced molecular packing and structural ordering. These optimized fibrous ordered structures enhance exciton dissociation, suppress charge recombination, and enable more balanced charge transport. Consequently, the optimized devices achieve a power conversion efficiency (PCE) of 20.18%.<\/jats:p>","DOI":"10.1002\/smtd.71089","type":"journal-article","created":{"date-parts":[[2026,9,30]],"date-time":"2026-09-30T09:57:33Z","timestamp":1790762253000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["An Optimized Fibrous Network by Collaborative Slowing Aggregation Kinetics and Enhancing Intermolecular Interactions via a Co\u2010Solvent Combined With Solid Additive Strategy Enables 20% Efficient Organic Solar Cells"],"prefix":"10.1002","author":[{"given":"Hanyue","family":"Gao","sequence":"first","affiliation":[{"name":"State Key Laboratory of Polymer Science and Technology Changchun Institute of Applied Chemistry Chinese Academy of Sciences  Changchun China"},{"name":"School of Applied Chemistry and Engineering University of Science and Technology of China  Hefei 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