Sulfur-containing reductant-based advanced oxidation processes (AOPs) are emerging as promising technologies for micropollutant removal. This project compares chlorite/sulfite (ClO2−/S(IV)) and ferrate/sulfite (Fe(VI)/S(IV)) AOPs in terms of micropollutant degradation, and reactive species generation. Both Fe(VI)/S(IV) and ClO2−/S(IV) demonstrated varying efficacy in removing 11 target pollutants, achieving 23–100% removal within 5 minutes under optimal conditions (oxidant: sulfite = 100: 500 μM, pH = 7.5). Compared to individual oxidants, the combined processes significantly enhanced micropollutant abatement, achieving removal rates 1.24–13.67 times higher. These results provide valuable guidance for the application of sulfite-based AOPs in wastewater treatment.