Iron electrocoagulation is designed for sustainable high-efficiency and high-flexibility water purification applications. Recent advances reported that hydroxyl radicals (•OH)-based oxidative transformation of organic contaminants can occur in iron electrocoagulation. However, there is still a lack of mechanistic understanding the production of •OH in bicarbonate electrolyte, which presents a critical knowledge gap in the optimization of iron electrocoagulation technology towards practical application. Combined with contaminant degradation, radical quenching experiments, and spectroscopic techniques, we found that •OH was produced at rate of 16.1 μM∙h ^− 1 during 30-mA iron electrocoagulation in bicarbonate electrolyte through activation of O₂ by Fe(II) under pH-neutral conditions. High yield of •OH occurred at pH 8.5, likely due to high adsorbed Fe(II) that can activate O₂ to enhance •OH production. Mössbauer and X-ray photoelectron spectroscopy measurements substantiated that Fe(II)-adsorbed lepidocrocite was the dominant solid Fe(II) species at pH 8.5. A process-based kinetic modeling was developed to describe the dynamic of •OH production, Fe(II) oxidation, and contaminant degradation processes in iron electrocoagulation. Findings of this study extend the functionality of electrocoagulation from phase separation to •OH-based advanced oxidation process, which provides a new perspective for the development of electrocoagulation-based next generation sustainable water purification technology.