Electrochemical water splitting is a promising technique for the production of high‐purity hydrogen. Substituting the slow anodic oxygen evolution reaction with an oxidation reaction that is thermodynamically more favorable enables the energy‐efficient production of hydrogen. Moreover, this approach facilitates the degradation of environmental pollutants and synthesis of value‐added chemicals through the rational selection of small molecules as substrates. Strategies for small‐molecule selection and electrocatalyst design are critical to electrocatalytic performance, with a focus on achieving a high current density, selectivity, Faradaic efficiency, and operational durability. This perspective discusses the key factors required for further advancement, including technoeconomic analysis, new reactor system design, meeting the requirements of industrial applications, bridging the gap between fundamental research and practical applications, and product detection and separation. This perspective aims to advance the development of hybrid water electrolysis applications.