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These reactions, broadly classified as alternative oxidation reactions (AOR), directly compete with the prevalent oxygen evolution reaction (OER). In molecular catalysis, the Oxo\u2010Wall dictates a transition from a stable oxo intermediate (OER active) to a meta\u2010stable metal\u2010oxo (OER inactive) generally occurs. In this work on heterogeneous catalysis, the same Oxo\u2010Wall applies, however, a meta\u2010stable oxo preferentially coordinates with lattice oxygen to form a more stable surface peroxo intermediate. A universal free energy onset of this process is identified at 3.39\u00a0eV under electrochemical activation in water and show that it is completely decoupled from the OER oxo species. Such decoupling gives rise to a new region of oxygen reactivity relevant for AOR where a selective oxidation of the unsaturated C\u2010C bonds is predicted to occur instead of OER. A distinct AOR overpotential volcano is constructed and identify recently reported electrocatalysts, including palladium\u2010platinum for propylene epoxidation and silver\u2010nickel for ethylene epoxidation, along with others such as TiO\n                    <jats:sub>2<\/jats:sub>\n                    and CuO. Broader implications and limitations of electrochemical AOR are discussed, highlighting their potential to enable electrochemically enhanced thermal catalysis.\n                  <\/jats:p>","DOI":"10.1002\/advs.202517229","type":"journal-article","created":{"date-parts":[[2025,11,4]],"date-time":"2025-11-04T18:15:55Z","timestamp":1762280155000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Crossing the Oxo\u2010Peroxo Wall for Selective Electrochemical Epoxidation"],"prefix":"10.1002","volume":"13","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9698-5067","authenticated-orcid":false,"given":"Pooja","family":"Basera","sequence":"first","affiliation":[{"name":"Department of Chemical Engineering Stanford University  Stanford CA 94305 USA"},{"name":"SUNCAT Center for Interface Science and Catalysis and Liquid Sunlight Alliance SLAC National Accelerator Laboratory  Menlo Park CA 94025 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