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However, the intrinsically low solubility of high\u2010molecular\u2010weight donor polymers in nonhalogenated solvents, particularly those with tightly packed, highly crystalline backbones such as the pinnacle of donor materials (D18), disrupts multiscale morphology evolution and severely limits device performance. Here, without compromising the polymer's molecular weight or its intrinsic propensity for ordered packing, we establish a copolymerized \u201cplasticizer\u201d strategy that enhances the solvation interaction between a nonhalogenated solvent (toluene) and an appended plasticizing comonomer, thereby improving the processability. By integrating a plasticizing unit (bis(2\u2010(2\u2010methoxyethoxy)ethyl) thieno[3,2\u2010\n                    <jats:italic>b<\/jats:italic>\n                    ]thiophene\u20103,6\u2010dicarboxylate) into the D18 backbone, the resulting D18\u2010O exhibits markedly enhanced solubility through dipolar interactions with toluene. These interactions suppress excessive pre\u2010aggregation, slow down crystallization kinetics of the donor, and ultimately guide the formation of well\u2010defined nanocrystals and a hierarchy of optimized morphologies during nonhalogenated processing. This approach enables both OSCs and modules processed from toluene to achieve record power conversion efficiencies of 20.78% (certified 20.40%) and 17.83% (certified 17.29%), respectively, along with exceptional stability.\n                  <\/jats:p>","DOI":"10.1002\/adma.73994","type":"journal-article","created":{"date-parts":[[2026,7,10]],"date-time":"2026-07-10T15:17:03Z","timestamp":1783696623000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Copolymerized Plasticizer Enables Halogen\u2010Free Processing Toward 20.78% and 17.83% Efficient Organic Solar Cells and Modules"],"prefix":"10.1002","volume":"38","author":[{"given":"Jiachen","family":"Zhang","sequence":"first","affiliation":[{"name":"Laboratory of Advanced Optoelectronic Materials Suzhou Key Laboratory of Novel Semiconductor\u2010Optoelectronics Materials and Devices State Key Laboratory of Bioinspired Interfacial Materials Science College of Chemistry Chemical Engineering and Materials Science Soochow University  Suzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hongxiang","family":"Li","sequence":"additional","affiliation":[{"name":"College of Materials and Energy Guang'an Institute of Technology  Guang'an China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Junyuan","family":"Ding","sequence":"additional","affiliation":[{"name":"Laboratory of Advanced Optoelectronic Materials Suzhou Key Laboratory of Novel Semiconductor\u2010Optoelectronics Materials and Devices State Key Laboratory of Bioinspired Interfacial Materials Science College of Chemistry Chemical Engineering and Materials Science Soochow University  Suzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jia","family":"Li","sequence":"additional","affiliation":[{"name":"Laboratory of Advanced Optoelectronic Materials Suzhou Key Laboratory of Novel Semiconductor\u2010Optoelectronics Materials 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