Sulfite has been proven to promote advanced oxidation processes (AOPs) to achieve low-cost and efficient degradation of contaminants, serving as an alternative to persulfate. In this study, a novel composite Fe/Mn@carbon felt (CF) electrode was successfully constructed to remove carbamazepine (CBZ). The capacity of the Fe/Mn@CF anode to activate sulfite was evaluated under various electrode preparation conditions and operating parameters. Results clearly indicated that the complete removal of CBZ was achieved in Fe/Mn@CF anode activated sulfite system under the specific conditions including Na2SO4 electrolyte concentration of 50 mM, sulfite dosage of 1 mM, initial pH of 7, and current density of 1 mA/cm2. The capacity of Fe/Mn@CF anode for sulfite activation was further presented by its excellent reusability and stability in terms of CBZ removal and metal ion release. Both radical and non-radical pathways were significantly contributed to the CBZ removal, including OH, SO4·-, O2·-, 1O2, and other reasons. Density functional theory (DFT) calculations demonstrated that Fe-Mn bimetals effectively promoted sulfite activation, with the electric field further boosting the process of Fe-Mn valence cycle and oxidation. Overall, the novel Fe/Mn@CF activated sulfite system exhibited outstanding performance and had great potential for sustainable use in removing organics.