Our research group is active in the development of oxidation protocols using o-iodoxybenzoic acid (IBX) and modified IBXs, and Oxone. In 2016, we have reported a facile protocol to access sulfonic acids using Oxone  or KBrO3. During the study, oxidation of thiols with hypervalent iodanes like phenyliodine bis(trifluoroacetate) (PIFA, λ 3 -iodane), o-iodoxybenzoic acid (IBX, λ 5 -iodane) and NaIO4 (λ 7 -iodane), afforded the disulfide in 8493% yields at rt. When a higher equivalent of the oxidant will be employed, the in situ generated disulfides should further be oxidized into symmetrical thiosulfonates in one-pot. We thus employed organo-λ 5 -iodanes, namely, IBX and Dess-Martin periodinane (DMP), for this tandem transformation of thiols to thiosulfonates. This hypervalent iodine (V) oxidants are well-known for their mild, user-and eco-friendly attributes, and are capable of executing myriads of transformations. As anticipated, the reactions of both DMP (1.2 equiv) and IBX (2.0 equiv) were found to serve the facile conversion of thiols to thiosulfonates at rt. For benzyl thiols, the reaction with DMP led to the formation of o-iodobenzoate, which were successfully and selectively converted to valuable functional groups such as aldehyde and alcohol. The detailed study and mechanistic insights are discussed below.