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However, the experimental detection of such oxides on well\u2010defined model electrodes under operando conditions is a major challenge, limiting our ability to establish clear structure\u2013performance relationships. Using surface\u2010sensitive total\u2010reflection X\u2010ray absorption spectroscopy in real time during cyclic voltammetry, combined with inductively coupled plasma mass spectrometry dissolution measurements, we demonstrate that an ultrathin (~5\u2009\u00c5) hydroxide film forms on the gold (111) surface prior to the onset of the oxygen evolution reaction. This film, composed of Au\n                    <jats:sup>3+<\/jats:sup>\n                    in similar coordination as in the bulk oxyhydroxide, thus governs its catalytic properties, dissolution, and restructuring. The results highlight the importance of surface oxidation in water splitting catalysis even for Au(111), the most inert surface of the most inert noble metal.\n                  <\/jats:p>","DOI":"10.1002\/cphc.70567","type":"journal-article","created":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T00:50:18Z","timestamp":1790643018000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["An Ultrathin Hydroxide Film Governs the Stability and Reactivity of Gold for the Oxygen Evolution Reaction"],"prefix":"10.1002","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-3132-4318","authenticated-orcid":false,"given":"A.","family":"Grespi","sequence":"first","affiliation":[{"name":"Division of Synchrotron Radiation Research Lund University  Lund Sweden"},{"name":"NanoLund Lund University  Lund Sweden"},{"name":"Department of Physics Techincal University of Denmark  Kongens Lyngby Denmark"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"A.","family":"Larsson","sequence":"additional","affiliation":[{"name":"Division of Synchrotron Radiation Research Lund University  Lund Sweden"},{"name":"NanoLund Lund University  Lund Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"A.","family":"Ti","sequence":"additional","affiliation":[{"name":"Division of Synchrotron Radiation Research Lund University  Lund Sweden"},{"name":"NanoLund Lund University  Lund Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8407-2260","authenticated-orcid":false,"given":"V.","family":"Briega\u2010Martos","sequence":"additional","affiliation":[{"name":"Helmholtz\u2010Institute Erlangen\u2010N\u00fcrnberg for Renewable Energy (IET\u20102) Forschungszentrum J\u00fclich GmbH  Erlangen Germany"},{"name":"Department of Interface Science Fritz Haber Institute of the Max Planck Society  Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0008-7001-8480","authenticated-orcid":false,"given":"E.","family":"Lira","sequence":"additional","affiliation":[{"name":"Division of Synchrotron Radiation Research Lund University  Lund Sweden"},{"name":"NanoLund Lund University  Lund Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0009-0056-3165","authenticated-orcid":false,"given":"U.","family":"K\u00fcst","sequence":"additional","affiliation":[{"name":"Division of Synchrotron Radiation Research Lund University  Lund Sweden"},{"name":"NanoLund Lund University  Lund Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0680-5454","authenticated-orcid":false,"given":"G.","family":"Abbondanza","sequence":"additional","affiliation":[{"name":"Division of Synchrotron Radiation Research Lund University  Lund Sweden"},{"name":"NanoLund Lund University  Lund Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7171-1385","authenticated-orcid":false,"given":"J.","family":"Manidi","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Materials and Chemical Engineering Politecnico di Milano  Milano Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7188-4857","authenticated-orcid":false,"given":"S.","family":"Cherevko","sequence":"additional","affiliation":[{"name":"Helmholtz\u2010Institute Erlangen\u2010N\u00fcrnberg for Renewable Energy (IET\u20102) Forschungszentrum J\u00fclich GmbH  Erlangen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7517-5089","authenticated-orcid":false,"given":"A.","family":"Shavorskiy","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Materials and Chemical Engineering Politecnico di Milano  Milano Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1128-7524","authenticated-orcid":false,"given":"M.","family":"Scardamaglia","sequence":"additional","affiliation":[{"name":"MAX IV Laboratory Lund University  Lund Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"M.","family":"Ramakrishnan","sequence":"additional","affiliation":[{"name":"MAX IV Laboratory Lund University  Lund Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1725-1677","authenticated-orcid":false,"given":"J.","family":"Just","sequence":"additional","affiliation":[{"name":"MAX IV Laboratory Lund University  Lund Sweden"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3213-4199","authenticated-orcid":false,"given":"L. 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