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Photoelectrocatalysis (PEC) offers a promising green route; however, its performance is limited by competitive adsorption and inadequate control over reaction selectivity. Herein, we engineered an asymmetric dual\u2010site earth\u2010abundant semiconductor to achieve biradical\u2010mediated C\u2013N coupling, attaining a Faradaic efficiency of 86.6%, a selectivity of 90.1%, and a DMF yield of 145.5\u00a0mmol\u00a0m\n                    <jats:sup>\u22122<\/jats:sup>\n                    \u00a0h\n                    <jats:sup>\u22121<\/jats:sup>\n                    . For practical implementation, the parallel\u2010connect stacked PEC device, with an area of 175\u00a0cm\n                    <jats:sup>2<\/jats:sup>\n                    , was recorded as the state\u2010of\u2010the\u2010art PEC system for DMF photoelectrosynthesis. Mechanistic investigations revealed that bismuth vacancies, possessing a high p\u2010band center, preferentially activated methanol to generate *CHO radicals, whereas BiO\n                    <jats:sub>x<\/jats:sub>\n                    sites, characterized by a moderate electronic environment, selectively catalyzed dimethylamine to form *N(CH\n                    <jats:sub>3<\/jats:sub>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    radicals. This dual\u2010site architecture effectively decouples the competitive adsorption of alcohol and amine substrates, enabling spatial segregation and achieving biradical\u2010mediated C\u2013N coupling. Importantly, the system demonstrated broad substrate adaptability, including cyclic secondary amines, highlighting its potential for constructing valuable amide derivatives. Our work provides a practical strategy for the mild valorization of biomass feedstocks and establishes an electronic structure\u2010guided paradigm for selectivity control and kinetic optimization in biradical\u2010mediated C\u2013N coupling.\n                  <\/jats:p>","DOI":"10.1002\/anie.9125401","type":"journal-article","created":{"date-parts":[[2026,8,22]],"date-time":"2026-08-22T09:46:26Z","timestamp":1787391986000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Asymmetric Dual Sites Enable Spatially Resolved Biradical\u2010Mediated C\u2013N Coupling for N,N\u2010Dimethylformamide Photoelectrosynthesis"],"prefix":"10.1002","volume":"65","author":[{"given":"Yuye","family":"Jiao","sequence":"first","affiliation":[{"name":"Frontiers Science Center for Smart Materials Oriented Chemical Engineering. 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