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However, its selectivity and activity are severely limited by uncontrollable over\u2010oxidation: Formaldehyde has lower C\u2010H dissociation energy than methane, prone to deep overoxidation to CO\n                    <jats:sub>2<\/jats:sub>\n                    . Herein, we report H\/WO\n                    <jats:sub>2.72<\/jats:sub>\n                    hydrogenated nonstoichiometric tungsten oxide photocatalyst. At ambient temperature, it attains 100% HCHO selectivity over all detectable carbonaceous products at 30.94 \u00b5mol\u00b7h\n                    <jats:sup>\u22121<\/jats:sup>\n                    , with 11\u2010fold higher activity than commercial WO\n                    <jats:sub>3<\/jats:sub>\n                    and outperforming most conventional photocatalysts. Operando spectroscopic studies and density functional theory (DFT) calculations reveal that surface W\u2010H bonds act as a kinetically gated \u201cAnti\u2010Overoxidation valve,\u201d W\u2013H bonds are preferentially cleaved by reactive oxygen species (\u00b7OOH), as they are thermodynamically weaker than the C\u2013H bonds in HCHO and its over\u2010oxidation intermediate (*HCOOH). Then the generated hydrogen radicals (H*) drive a reverse reduction pathway to convert the *HCOOH back to *HCHO, interrupting deep oxidation. Concurrently, hydrogenation optimizes the electronic structure of WO\n                    <jats:sub>2.72<\/jats:sub>\n                    , lowering the HCHO desorption barrier to facilitate timely product release. This work provides a dynamic strategy for complete selectivity in catalytic CH\n                    <jats:sub>4<\/jats:sub>\n                    conversion, emphasizing the value of precise kinetic pathway modulation for methane valorization.\n                  <\/jats:p>","DOI":"10.1002\/anie.2226950","type":"journal-article","created":{"date-parts":[[2026,10,2]],"date-time":"2026-10-02T07:36:27Z","timestamp":1790926587000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["W\u2013H Bond\u2010Mediated \u201cAnti\u2010Overoxidation Valve\u201d: 100% Formaldehyde Selectivity Among Detected Products in Photocatalytic Methane\u2010to\u2010Formaldehyde Conversion"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-8418-107X","authenticated-orcid":false,"given":"Rui","family":"Li","sequence":"first","affiliation":[{"name":"Shanxi Key Laboratory of Complex Air Pollution Control and Carbon Reduction 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