A facile methodology for the conversion of thiols to thiosulfonates has been developed employing IBX and DMP. The oxidations can be achieved employing DMP (1.2 equiv)/DCM or IBX (2.0 equiv)/MeCN at rt (30 C), and a variety of thiosulfonates can be accessed. DMP-mediated oxidation of benzyl thiols do not afford thiosulfonates, but lead to esters of o-iodobenzoic acid. The latter can be further explored for tandem transformations into aldehyde and alcohol. This is the first report of thiol to alcohol conversion using hypervalent iodine reagents. Mechanistic investigation through 1 H NMR spectroscopic monitoring reveals that the oxidations proceed through the formation of intermediary disulfides; the latter evidently undergo a cascade of oxidations with either I(V) or I(III) species to furnish thiosulfonates. In view of the fact that thiosulfonates have vast applications, we believe that this methodology will constitute an invaluable addition to the transformations mediated by hypervalent iodine compounds.