o-Iodoxybenzoic acid (IBX) has recently emerged as a mild and environmentally friendly oxidizing agent capable of effecting the oxidations of a variety of functional groups including the selective oxidation of benzylic C-H bonds. An enthalpically favored H-atom abstraction from the benzylic site followed by a single electron transfer (SET) step to produce a benzylic carbocation was speculated as a plausible mechanism by us for the selective oxidation at the benzylic carbon. In this study, we demonstrate the capture of the proposed benzyl carbocation intermediate by potassium persulfate (KHSO₅) present in Oxone to give a peroxyester intermediate (shown inside the box below) which decomposes to produce the observed oxidized products. The benign nature of IBX and Oxone and the aqueous solvent system used makes the procedure environmentally-friendly.