In response to the pressing global challenge of water scarcity, we present a pioneering multiple-benefit electrolytic cell that seamlessly integrates electrodialysis desalination, isopropanol valorization, H2 production, and energy saving within a single, unified platform. This is realized through an innovative three-chamber design, in which anodic isopropanol oxidation in an alkaline environment is coupled with cathodic hydrogen evolution in acid, synergistically driving efficient and sustainable desalination. To this end, a finely engineered phosphorus-modified NiMo-oxide catalyst (NiMoO-P@Ni-350) is developed to achieve highly selective conversion of isopropanol into value-added acetone with outstanding efficiency, delivering a current density of 10 mA cm−2 at just 1.3 V and exceeding 90% faradaic efficiency. Systematic analyses reveal favorable dynamic reconstruction of the catalyst and uncover an indirect oxidation mechanism, providing deep insights into its exceptional catalytic performance. Furthermore, the triple-benefit electrolytic cell demonstrates stable operation at a low voltage of 0.6 V, achieving over 90% NaCl removal over 168 h of continuous operation. This work not only addresses the pressing demand for clean water but also advances electrochemical technology by seamlessly integrating purification, energy generation, and carbon valorization into a unified, sustainable platform.