Microbial advanced oxidation, a fundamental process for pollutant degradation in nature, is limited in efficiency by the weak respiration of indigenous microorganisms. In this study, an electric field was employed to enhance microbial respiration and facilitate the microbial advanced oxidation of p-nitrophenol (PNP) in simulated wetlands with alternation of anaerobic and aerobic conditions. With intermittent air aeration, an electric field of 0.8 V promoted extracellular electron transfer to increase Fe2+ generation through dissimilatory iron reduction and the production of hydroxyl radicals (•OH) through Fenton-like reactions. As a result, the PNP removal rate of the electrically-stimulated group was higher than that of the control (72.15 % vs 46.88 %). Multiple lines of evidence demonstrated that the electrically-induced polarization of respiratory enzymes expedited proton-coupled electron transfer within the respiratory chain to accelerate microbial advanced oxidation of PNP. The polarization of respiratory enzymes with the electric field hastened proton outflow to increase cell membrane potential for adenosine triphosphate (ATP) generation, which enhanced intracellular electron transportation to benefit reactive oxygen species generation. This study provided a new method to enhance microelectrochemical remediation of the contaminant in wetlands via the combination of intermittent air aeration.