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Here, we introduce a dual\u2010asymmetric topology strategy, in which the stereochemical configurations of both the central core and terminal groups are co\u2010engineered. Using this approach, we synthesized an isomeric pair, Th2Cl\u2010a\u20102Cl and Th2Cl\u2010b\u20102Cl and benchmarked them against the singly asymmetric a\u2010CH\u2010Th2Cl and Th2Cl\u20104Cl. We find that the distinctive steric conformation of Th2Cl\u2010a\u20102Cl promotes a geometrically complementary, interlocked packing motif within the crystal lattice. This not only reinforces the three\u2010dimensional network connectivity but, more importantly, gives rise to a more uniform local electrostatic environment at the molecular\u2010skeleton scale. As a result, Th2Cl\u2010a\u20102Cl exhibits weaker and more balanced environment\u2010induced electrostatic fluctuations along the backbone, which helps reduce local electrostatic perturbations during charge transport. Consequently, PM6:Th2Cl\u2010a\u20102Cl devices deliver a champion PCE of 20.18% with a high fill factor (FF) of 80.88%, while significantly suppressing the non\u2010radiative recombination loss (\u0394\n                    <jats:italic>E<\/jats:italic>\n                    <jats:sub>3<\/jats:sub>\n                    ) to 0.190\u00a0eV. These results establish geometric complementarity and electrostatic homogeneity, achieved through topological engineering, as an effective route to improve the efficiency of OSCs.\n                  <\/jats:p>","DOI":"10.1002\/adma.74732","type":"journal-article","created":{"date-parts":[[2026,8,21]],"date-time":"2026-08-21T05:09:36Z","timestamp":1787288976000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Geometric Complementarity and Electrostatic Fluctuation Control in Dual\u2010Asymmetric Acceptors for Efficient Organic Solar Cells"],"prefix":"10.1002","volume":"38","author":[{"given":"Jiye","family":"Chen","sequence":"first","affiliation":[{"name":"State Key Laboratory of Elemento\u2010Organic Chemistry Frontiers Science Center For New Organic Matter  China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ruohan","family":"Wang","sequence":"additional","affiliation":[{"name":"State Key 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