A 1:1 supramolecular complex (met-hemoCD) of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrinatoiron(III) ((FeTPPS)-T-III) with a per-O-methylated beta-cyclodextrin dimer having a -SCH2PyCH2S- (Py = pyridin-3,5-diyl) linker (Py3CD) reacted rapidly with hydrogen peroxide or cumene hydroperoxide in an aqueous solution forming two types of hydroperoxo or alkylperoxo intermediates, ROO-Fe-III(OH-)PCD and ROO-Fe-III(Py)PCD, which underwent rapid homolysis to the corresponding ferryloxo species, namely, O=Fe-IV(OH-)PCD and O=Fe-IV(Py)PCD, respectively. For the O=Fe-IV(OH-)PCD species, the iron-oxo oxygen facing the linker gradually transferred to the nearby sulfide bond on the linker, forming the sulfoxidized Py3CD (Py3CD-O)/(FeTPPS)-T-II complex, which then bound dioxygen in air forming an oxy-ferrous complex, O-2-(FeTPPS)-T-II/Py3CD-O. In contrast, the O=Fe-IV(Py)PCD species, in which the iron-oxo oxygen was located on the opposite side of the sulfide bond on the linker across the porphyrin ring, was reduced to the resting state (met-hemoCD) by the surroundings without any oxidation of the Py3CD linker.