In this study, reductive sulfite (S(IV)) was innovatively introduced into activated carbon fibers supported ferric citrate (Cit-Fe@ACFs) and persulfate (PS) process for organic dye removal. The addition of S(IV) enhanced the catalytic elimination rate of organic dye Reactive Red M-3BE from 15.2% to 96.2% in 12min (kobs (pseudo-first-order rate constant) from 0.015 to 0.324min−1). More importantly, the simultaneous removal of S(IV), which is a common inorganic pollutant, was also achieved. This Cit-Fe@ACFs/S(IV)/PS system exhibited superior sustained catalytic ability and distinguished pH-tolerant performance for the simultaneous rapid removal of dyes and inorganic S(IV). Furthermore, the reaction rate constant (kobs) increased with the increase of concentration of S(IV) below 1mM, while decreased over 1mM. Finally, various radical scavengers were used together with electron paramagnetic resonance spectroscopy to confirm that hydroxyl (OH), sulfate (SO4−) and peroxymonosulfate (SO5−) radicals served as the major reactive oxygen species in the Cit-Fe@ACFs/S(IV)/PS system. This study provides a promising idea to use polluting S(IV) in sewage treatment for the simultaneous removal of organic and inorganic pollutants.