Sulfate radical-based advanced oxidation processes driven by sulfite [S(IV)] activation offer a sustainable and cost-effective approach for environmental remediation. The utilization of abundant iron oxide species in Fe-rich sludge for S(IV) activation presents a cost-effective and eco-friendly solution, making it an attractive option for Fe-rich sludge disposal and water treatment. Herein, an efficient S(IV) activation system was developed by using Fe-rich sludge-derived biochar (FBC) for the first time. The performance of S(IV) activation by different pyrolyzed FBCs was evaluated in terms of tetracycline (TC) degradation. The highest degradation efficiency of TC was achieved 95.0 % in the S(IV)/FBC700 under the optimum conditions. The reactive radical species responsible for TC degradation in the system were confirmed to be SO4•−. The present work opens up new possibilities for the development of novel advanced oxidation processes utilizing the waste Fe-rich sludge.