AbstractElectro‐oxidation (EO) technology demonstrates significant potential in wastewater treatment. However, the high energy consumption has become a pivotal constraint hindering its large‐scale implementation. Herein, we design an EO and 4‐electron oxygen reduction reaction coupled system (EO‐4eORR) to replace the traditional EO and hydrogen evolution reaction (HER) coupled system (EO‐HER). The theoretical cathodic potential of the electrolytic reactor is tuned from 0 V (vs. RHE) in HER to 1.23 V (vs. RHE) in 4eORR, which greatly decreases the required operation voltage of the reactor. Moreover, we demonstrate that convection can improve the mass transfer of oxygen and organic pollutants in the reaction system, leading to low cathodic polarization and high pollutant removal rate. Compared with traditional EO‐HER system, the energy consumption of the EO‐4eORR system under air aeration for 95 % total organic carbon (TOC) removal is greatly decreased to 2.61 kWh/kgTOC (only consider the electrolyzer energy consumption), which is superior to previously reported EO‐based water treatment systems. The reported results in this study offer a new technical mode for development of highly efficient and sustainable EO‐based treatment systems to remove organic pollutants in waste water.