Abstract: Driven by the rapid decline in renewable energy generation costs and the “dual carbon” goals, electrocatalytic water splitting powered by renewable electricity is increasingly becoming a vital method for producing high-purity hydrogen. However, the sluggish kinetics of the anodic four-electron oxygen evolution reaction(OER) significantly limit the overall energy efficiency of the process. By replacing conventional OER small molecule oxidation reactions that have lower thermodynamic barriers, low-energy- hydrogen production can be achieved, while simultaneously enabling the generation of high-value-added chemicals at the anode or the degradation and resource recovery of pollutants. Recent advances in coupled systems for electrocatalytic hydrogen evolution and organic/inorganic small molecule oxidation reactions are summarized, with a focus on catalyst design strategies, structure-activity relationships, and catalytic mechanisms under different alternative reaction pathways. Finally, future research directions and key challenges in this field are discussed, providing insights for advancing efficient and economical large-scale green hydrogen production.