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In this study, we developed a disulfide\u2010linked dimeric acceptor, DY\u2010SS, by integrating an exchangeable dynamic covalent linkage into the backbone of a photoactive acceptor, representing, to our knowledge, the first photoactive material framework containing exchangeable dynamic covalent linkages. DY\u2010SS acts as an energetic and morphological regulator, reducing non\u2010radiative energy loss, modulating crystallization kinetics, and enhancing molecular packing coherence. Consequently, the ternary devices achieve a high PCE of 20.40%, compared with 19.64% for the binary control, accompanied by a 1.62\u2010fold extension of the\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>80<\/jats:sub>\n                    thermal lifetime. In the presence of trace thioctic acid, thermally activated disulfide exchange enables the formation of an adaptive covalent network, which promotes stress dissipation and markedly improves film toughness and yielding a markedly increased crack\u2010onset strain of 16.07% (3.89\u2010fold over the binary control) and a 7.54\u2010fold enhancement in toughness. Notably, the toughened flexible OSCs demonstrate unprecedented mechanical durability, retaining 91.1% of their initial efficiency even after 10\n                    <jats:sup>5<\/jats:sup>\n                    bending cycles under the extreme condition of a 1\u00a0mm bending radius (vs. 82.1% for the control). This work provides a dynamic\u2010bond\u2010containing molecular design strategy for efficient and mechanically robust OSCs.\n                  <\/jats:p>","DOI":"10.1002\/anie.5303924","type":"journal-article","created":{"date-parts":[[2026,8,6]],"date-time":"2026-08-06T11:30:36Z","timestamp":1786015836000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Dynamic Disulfide\u2010Linked Dimeric Acceptors for High\u2010Efficiency and Mechanically Robust Organic Solar Cells"],"prefix":"10.1002","volume":"65","author":[{"given":"Yang","family":"Cheng","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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China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bo","family":"Wang","sequence":"additional","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. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0003-1618-8618","authenticated-orcid":false,"given":"Yao","family":"Li","sequence":"additional","affiliation":[{"name":"Thrust of Advanced Materials The Hong Kong University of Science and Technology (Guangzhou) Nansha  Guangzhou P. R. 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