Abstract: The design of effective hydrogen generation systems with low energy consumption is pivotal for sustainable energy conversion. The slow oxygen evolution reaction hinders conventional water electrolysis, resulting in high energy consumption. Combining the processes of hydrogen evolution reaction (HER) and alcohol oxidation reaction (AOR) provides an effective approach involves substituting the oxygen evolution reaction with more energetically favourable organic oxidation reaction, which can achieve lower cell voltages and simultaneous production of value-added chemicals. Recent advances in electrocatalyst design including nanostructured, bimetallic, and atomically dispersed systems have significantly enhanced catalytic performance through optimized adsorption energetics and improved charge transfer kinetics. Rational control over composition, morphology, and electronic structure is vital for enhanced activity, selectivity, and long-term durability. In addition, in-situ characterization techniques provide vital insights into catalyst reconstruction and active phase evolution under working conditions. This review outlines the recent progress in the rational design of electrocatalysts for HER–AOR systems, highlighting the role of in situ studies in elucidating structure–activity relationships and providing insight into their potential applications in efficient hydrogen production and organic transformations with reduced energy consumption.