Beyond Oxygen Evolution: Anodic High‐Value Conversion for Energy‐Saving Hydrogen and Chemical Co‐Production

ABSTRACT Water electrolysis offers a scalable route to green hydrogen, but its anodic half‐reaction is still constrained by the oxygen evolution reaction (OER), a sluggish four‐electron process that consumes voltage while yielding low‐value O 2 . Anodic high‐value conversion (AHVC) replaces this value‐losing step with product‐forming oxidation, enabling hydrogen evolution to be coupled with upgrading of oxygenated organics, nitrogen‐containing molecules, pollutants, and polymer or waste‐derived streams. Yet the promise of AHVC is not established by lower oxidation potential alone. Useful co‐production requires selective bond transformation, suppression of overoxidation and OER re‐entry, controlled intermediate fate, limited crossover, and recoverable product streams at relevant current densities. This Review develops a value‐retention framework for AHVC. We discuss the thermodynamic and kinetic origins of alternative anodic reactions, compare major substrate families and their product windows, and examine how working phases, interfacial adsorption, reactive oxygen species, and local microenvironments steer molecular pathways. Device translation is then considered through full‐cell metrics, membrane transport, product recovery, durability, and techno‐economic boundaries. By connecting molecular selectivity with electrolyzer operation, AHVC is framed as a route to energy‐saving hydrogen and value‐added chemical co‐production, rather than a simple OER substitute.