It is well documented that the traditional Fenton reagent (i.e., the combination of Fe(II) and H<sub>2</sub>O<sub>2</sub>) produces hydroxyl radical (<sup>•</sup>OH) under acidic conditions, while at near-neutral pH the reactive intermediate converts to ferryl ion (Fe(IV)) that can oxidize sulfoxides to produce corresponding sulfones, markedly differing from their <sup>•</sup>OH-induced products. However, it remains unclear whether Fe(IV) is generated in the Fe(II) activated peroxydisulfate (PDS) process, where sulfate radical (SO<sub>4</sub><sup>•-</sup>) is long recognized as the dominant intermediate in literature. Here we demonstrated that SO<sub>4</sub><sup>•-</sup> oxidized methyl phenyl sulfoxide (PMSO, a model sulfoxide) to produce biphenyl compounds rather than methyl phenyl sulfone (PMSO<sub>2</sub>). Interestingly, the formation of PMSO<sub>2</sub> was observed when PMSO was treated by the Fe(II)/PDS system over a wide pH range, and the yields of PMSO<sub>2</sub> were quantified to be ∼100% at acidic pH 3-5. The identification of Fe(IV) in the Fe(II)/PDS system could also reasonably explain the literature results on alcohol scavenging effect and ESR spectra analysis. Further, a Fe(IV)-based kinetic model was shown to accurately simulate the experimental data. This work urges re-evaluation of the Fe(II)/PDS system for environmental decontamination, given that Fe(IV) would have different reactivity toward environmental contaminants compared with SO<sub>4</sub><sup>•-</sup> and/or <sup>•</sup>OH.