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Herein, it is reported that a copper(I) salt efficiently converts CO<jats:sub>2<\/jats:sub> into methanol equivalent in the presence of NaBH<jats:sub>4<\/jats:sub> and an amide ligand (L1) under mild reaction conditions. The in\u2009situ generated active catalyst in the reaction is isolated as a single crystal and the structure solution reveals the formation of a reactive two\u2010coordinate Cu(I) dimeric catalyst [Li<jats:sub>2<\/jats:sub>(THF)<jats:sub>4<\/jats:sub>Cu(L1)<jats:sub>4<\/jats:sub>] <jats:bold>(1)<\/jats:bold>. The key transient species \u201ccopper\u2010hydride\u201d responsible for the CO<jats:sub>2<\/jats:sub> to methanol equivalent via [<jats:bold>1<\/jats:bold>\u2010BX<jats:sub>4<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> (where <jats:italic>X<\/jats:italic>\u2009=\u2009H or D) adduct formation is indirectly confirmed through NMR spectroscopy. The copper catalyst <jats:bold>(1)<\/jats:bold> shows a remarkable TON (3993) and TOF (166\u2009h<jats:sup>\u22121<\/jats:sup>) and remains active for more than 7 cycles with an overall TON of 10199. The mechanistic studies, supported by the characterization of key intermediates, provide a plausible pathway for this transformation.<\/jats:p>","DOI":"10.1002\/cssc.202500735","type":"journal-article","created":{"date-parts":[[2025,7,14]],"date-time":"2025-07-14T14:38:18Z","timestamp":1752503898000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Unlocking Key Intermediates in Copper\u2010Catalyzed CO<sub>2<\/sub> to Methanol Conversion"],"prefix":"10.1002","volume":"18","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0323-0771","authenticated-orcid":false,"given":"Vasudha","family":"Sharma","sequence":"first","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Bombay  Powai Mumbai Maharashtra 400076 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rajashi","family":"Haldar","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute 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