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Here, we identify severe aging\u2010driven Ag diffusion as a critical failure pathway in high\u2010efficiency conventional architectures. To suppress this without compromising charge extraction, we introduce polymethyl methacrylate (PMMA) that self\u2010assembles into a discontinuous, mesh\u2010like network on the PDINN layer, functioning as both a physical diffusion barrier and a chemical metal\u2010capture mesh. Spectroscopic analyses reveal that PMMA carbonyl groups coordinate with Ag through Ag\u2010O interactions, providing chemical immobilization that complements the physical barrier in blocking thermally activated, concentration\u2010gradient\u2010driven migration. Therefore, PMMA\u2010modified devices deliver a power conversion efficiency (PCE) of 20.2% with markedly enhanced stability: they retain &gt;80% of the initial PCE after 3,574\u00a0h under ISOS\u2010D\u20101I shelf storage, show a\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>80<\/jats:sub>\n                    of 105\u00a0h under ISOS\u2010D\u20102I thermal aging at 85\u00b0C, compared with only 10\u00a0h for control devices, and retain 70.1% after 94\u00a0h under ISOS\u2010L\u20103 conditions (1 sun, 65\u00b0C, 50% relative humidity), versus 51.4% for controls. This strategy also improves the thermal stability of Cu\u2010 and Au\u2010based devices, establishing a broadly applicable interfacial concept for mitigating electrode\u2010diffusion\u2010induced failure in high\u2010efficiency conventional OPVs.\n                  <\/jats:p>","DOI":"10.1002\/adma.74521","type":"journal-article","created":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T10:57:07Z","timestamp":1785927427000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Suppressing Electrode Diffusion With a PMMA Metal\u2010Capture Mesh Enables Stable Conventional Organic Photovoltaics"],"prefix":"10.1002","volume":"38","author":[{"given":"Qianqian","family":"Qi","sequence":"first","affiliation":[{"name":"College of Polymer Science and Engineering State Key Laboratory of Advanced Polymer Materials Sichuan University  Chengdu 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Science and Technology for Carbon Peak &amp; Neutrality School of Physical Science &amp; Technology Guangxi University  Nanning China"},{"name":"State Key Laboratory of Featured Metal Materials and Life\u2010cycle Safety for Composite Structures Guangxi University  Nanning China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2078-2778","authenticated-orcid":false,"given":"Xiaopeng","family":"Xu","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering and State Key Laboratory of Advanced Polymer Materials Sichuan University  Chengdu China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0536-2313","authenticated-orcid":false,"given":"Qiang","family":"Peng","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering and State Key Laboratory of Advanced Polymer Materials Sichuan University  Chengdu 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