Sulfur(IV) as a ubiquitous substance in the atmosphere and water bodies can be deliberately involved in different redox reactions based on the known ability to donate electrons, but the inhibition effect on the advanced oxidation processes (AOPs) especially the Fenton reaction, which played a vital role in aerosol aging and pollution treatment, still stayed fuzzy. In this work, it was first found that sulfite had an unexpected reactivity to accept electrons from Fe(II) monitored by the chemiluminescence (CL) method to reduce Fe(II) seriously. Dynamics calculation, UV–vis absorption, HPLC, and CL analysis indicated that sulfite anions can be transferred into SO2·- or dimer S2O42- through reacting with Fe(II). The direct consumption of Fe(II) in Fenton reaction only happened by sulfite among other inorganic anions during degrading different organic pollution, and the produced S2O42- showed an overpowering inhibitory ability on hydroxyl radical especially at pH 5.3, both resulting in a strong inhibition effect on the Fenton reaction. In contrast at pH 3.1, the fast depletion of sulfite by H2O2 and decomposition of S2O42- fell off the inhibition effect. Furthermore, abatement experiments showed that the effect of sulfite could be circumvented by using a non-iron-based oxidation system with other metal ions, additionally clarifying the reaction of Fe(II)-sulfite played the primary role in the inhibition. Significantly, this inhibition effect of sulfite on the Fenton reaction was demonstrated to take place both in the natural wastewater and degrading two acids from biomass burning in the atmosphere, identifying the attenuated Fenton reaction in the presence of sulfur(IV) in the environment.