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As electrosynthesis capability advances towards high\u2010purity products, the traditional proximity of reaction products to the electrode surface, where the reaction happens, increasingly becomes a limiting factor. In addition, the formation and transport of reactive species are confined in the same chamber, resulting in electrolyte contamination of the product. Porous solid electrolyte (PSE) reactors address this spatial constraint by introducing an additional ion\u2010conductive middle layer between the cathode and anode, enabling a versatile off\u2010electrode space for product formation and transportation. Here, we frame PSE reactors as function\u2010oriented platforms for off\u2010electrode electrosynthesis, in which the PSE middle layer serves as a functional reaction space that enables ionic recombination, reaction\u2010environment regulation, and improved management of reactive intermediates. By linking the underlying ionic\u2010species transport mechanisms and reactor design principles, we establish a structure\u2010transport\u2010function framework for understanding how PSE reactors extend electrosynthesis beyond the electrode surface confinement and guide the rational design of scalable electrosynthesis reactors as on\u2010site chemical manufacturing platforms.<\/jats:p>","DOI":"10.1002\/anie.5622879","type":"journal-article","created":{"date-parts":[[2026,8,29]],"date-time":"2026-08-29T04:48:58Z","timestamp":1787978938000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Porous Solid Electrolyte Reactors for Function\u2010Oriented Off\u2010Electrode Electrosynthesis"],"prefix":"10.1002","author":[{"given":"Xiu","family":"Lin","sequence":"first","affiliation":[{"name":"School of Materials Science and Engineering Nanyang Technological University  Singapore Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0765-5766","authenticated-orcid":false,"given":"Leonhard","family":"Tannesia","sequence":"additional","affiliation":[{"name":"School of Materials Science and Engineering Nanyang Technological University  Singapore Singapore"},{"name":"Nanyang Environment and Water Research Institute (NEWRI), Interdisciplinary Graduate Programme Nanyang Technological University  Singapore Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Li","family":"An","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Frontiers Science Center For Rare Isotopes, College of Chemistry and Chemical Engineering Lanzhou University  Lanzhou P. 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