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Here, we designed Cu\n                    <jats:sub>1<\/jats:sub>\n                    \u2010NC anchored on a carbon support featured with a high pyrrolic\u2010N to pyridinic\u2010N ratio (CuN\n                    <jats:sub>4<\/jats:sub>\n                    \/pr\u2010h\u2010NC), which enables an exceptional Faradaic efficiency (FE) of 79.6% for ethanol. Experimental and theoretical studies reveal that pyrrolic\u2010N and pyridinic\u2010N synergize with Cu sites to form novel triadic sites, which regulate the potential\u2010determining step (PDS) from the traditional C\u2013C coupling step to the protonation step of *CO to *COH. Pyrrolic N boosts *CO surface coverage, after which *CO migrates to neighboring pyridinic N sites for hydrogenation to *COH. The resulting *COH readily couples with another *CO at the single Cu site, driving selective ethanol formation. Due to the single\u2010metal\u2010surface\u2010independence of PDS, this mechanism extends to metals traditionally considered inactive for C\u2013C coupling (M = Fe, Co, Ni, Zn). A positive correlation is observed between the ethanol FE and the pyrrolic N\/pyridinic N ratio across the series, with ZnN\n                    <jats:sub>4<\/jats:sub>\n                    \/pr\u2010h\u2010NC reaching 71.8% at \u20130.5\u00a0V versus\u00a0RHE. This work establishes an ensemble site engineering strategy to rationally steer CO\n                    <jats:sub>2<\/jats:sub>\n                    to ethanol pathways for M\n                    <jats:sub>1<\/jats:sub>\n                    \u2010NC electrocatalysts.\n                  <\/jats:p>","DOI":"10.1002\/anie.8481946","type":"journal-article","created":{"date-parts":[[2026,7,21]],"date-time":"2026-07-21T12:18:23Z","timestamp":1784636303000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Triadic Sites Drive Tandem CO\n                    <sub>2<\/sub>\n                    \u2010to\u2010Ethanol Conversion by Steering *CO Coverage and *COH Intermediate Formation"],"prefix":"10.1002","volume":"65","author":[{"given":"Fang","family":"Zhao","sequence":"first","affiliation":[{"name":"Key Laboratory of Cluster Science Beijing Key Laboratory of Construction\u2010Tailorable Advanced Functional Materials and Green Applications School of Chemistry and Chemical Engineering Beijing Institute of Technology  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bo","family":"Huang","sequence":"additional","affiliation":[{"name":"Key Laboratory of Cluster Science Beijing Key Laboratory of Construction\u2010Tailorable Advanced Functional Materials and Green Applications School of Chemistry and Chemical Engineering Beijing Institute of Technology  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Huayi","family":"Kuang","sequence":"additional","affiliation":[{"name":"Department of Chemistry Engineering Research Center of Advanced Rare Earth Materials Tsinghua University  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lirong","family":"Zheng","sequence":"additional","affiliation":[{"name":"Beijing Synchrotron Radiation Facility Chinese Academy of Sciences  Beijing 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