Overall water splitting (OWS) to produce hydrogen has attracted large attention in recent years due to its ecological-friendliness and sustainability. However, the efficiency of OWS has been forced by the sluggish kinetics of the four-electron oxygen evolution reaction (OER). The replacement of OER by alternative electrooxidation of small molecules with more thermodynamically favorable potentials may fundamentally break the limitation and achieve hydrogen production with low energy consumption, which may also be accompanied by the production of more value-added chemicals than oxygen or by electrochemical degradation of pollutants. This review critically assesses the latest discoveries in the coupled electrooxidation of various small molecules with OWS, including alcohols, aldehydes, amides, urea, hydrazine, etc. Emphasis is placed on the corresponding electrocatalyst design and related reaction mechanisms (e.g., dual hydrogenation and N-N bond breaking of hydrazine and C═N bond regulation in urea splitting to inhibit hazardous NCO