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Electrochemical reduction offers a milder alternative, yet commonly stops at the alcohol stage because the initially formed alcohol intermediate desorbs from the electrode before further C\u2500O bond activation. Here, we report a \u2010Gly interfacial catalytic system for aqueous electrochemical carbonyl\u2010to\u2010methylene conversion. In this system, the Pd\u2010rich  electrode and glycine\u2010mediated interfacial regulation cooperate to retain alcohol intermediates at the electrified interface and promote their subsequent deoxygenation to methylene products. Time\u2010dependent reaction analysis supports a stepwise pathway involving initial carbonyl hydrogenation to an alcohol intermediate followed by further deoxygenation. Mechanistic and structural studies suggest that Pd sites supply surface H*, electron\u2010deficient Ni\u2010related sites generated through Ni\u2500Pd coordination assist alcohol\u2010intermediate retention, and glycine regulates local proton availability and H* coverage in the interfacial region. This work highlights the \u2010Gly system as an effective interfacial platform for directing carbonyl electroreduction beyond the alcohol endpoint under mild aqueous\u00a0conditions.<\/jats:p>","DOI":"10.1002\/anie.7784249","type":"journal-article","created":{"date-parts":[[2026,6,13]],"date-time":"2026-06-13T16:48:17Z","timestamp":1781369297000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Interfacial Proton Ordering Near the Electrode Surface Directs Carbonyl Electroreduction to Methylene"],"prefix":"10.1002","volume":"65","author":[{"given":"Hongliang","family":"Fan","sequence":"first","affiliation":[{"name":"State Key Laboratory of Advanced Chemical Power Sources, School of Chemistry and Chemical Engineering Chongqing University Chongqing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Baijing","family":"Wu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Chemical Power Sources, School of Chemistry and Chemical Engineering Chongqing University Chongqing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4496-0057","authenticated-orcid":false,"given":"Minhua","family":"Shao","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biological Engineering The Hong Kong University of Science and Technology Kowloon Hong Kong"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5912-2980","authenticated-orcid":false,"given":"Cunpu","family":"Li","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Chemical Power Sources, School of Chemistry and Chemical Engineering Chongqing University Chongqing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-9243-7979","authenticated-orcid":false,"given":"Zidong","family":"Wei","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Advanced Chemical Power Sources, School of Chemistry and Chemical Engineering Chongqing University Chongqing 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