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Here we introduce a switchable dual\u2010ligand strategy that decorates an identical Cu\n                    <jats:sub>13<\/jats:sub>\n                    H\n                    <jats:sub>10<\/jats:sub>\n                    core with tailored thiolate (\u2010SR) and phosphine (\u2010PR\n                    <jats:sub>3<\/jats:sub>\n                    ) ligands, creating three isostructural catalysts (NC1 to NC3) whose surface electronics diverge by design. A single\u2010step change in electron\u2010withdrawing ligand flips selectivity from C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    (Faradaic efficiency,\n                    <jats:italic>FE<\/jats:italic>\n                    <jats:sub>C2H4<\/jats:sub>\n                    \u2248 33 %) to EtOH (\n                    <jats:italic>FE<\/jats:italic>\n                    <jats:sub>EtOH<\/jats:sub>\n                    \u2248 31 %) without sacrificing \u2265 \u22120.2 A\u00b7cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    current density. In situ ATR\u2010SEIRAS and DFT reveal that \u2010SR ligands accelerate *COCHO\u2009\u2192\u2009*CCO dehydration toward C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    , whereas electron\u2010withdrawing \u2010PR\n                    <jats:sub>3<\/jats:sub>\n                    ligands stabilize *COCH\n                    <jats:sub>2<\/jats:sub>\n                    O route to EtOH. These insights deliver a clear design rule: modulate Cu\n                    <jats:sup>\u1e9f+<\/jats:sup>\n                    sites through ligand induction to program C\u2500C coupling pathways on demand.\n                  <\/jats:p>","DOI":"10.1002\/smll.202514571","type":"journal-article","created":{"date-parts":[[2026,1,14]],"date-time":"2026-01-14T09:54:28Z","timestamp":1768384468000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Manipulating the C\u2500C Coupling Pathway via Switchable Dual\u2010Ligand Mediation in Copper(I) Nanoclusters for Selective CO\n                    <sub>2<\/sub>\n                    Electroreduction to Ethylene\/Ethanol"],"prefix":"10.1002","volume":"22","author":[{"given":"Yang","family":"Zuo","sequence":"first","affiliation":[{"name":"College of Materials Science and Engineering Qingdao University of Science and Technology  Qingdao P. R. 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