In this work, the pro-oxidant behavior of oleuropein (OLP, 1) is characterized in a Fenton-like experiment by means of ESR spectroscopy using the spin trap system DMSO and 4-(pyridyl-1-oxide)-N-tert-butyl nitrone (POBN) in phosphate buffer (PB) solution. Ferrous ions in the absence of hydrogen peroxide cause the formation of the stable nitroxide species 4 and 5 through the intermediate perferryl species. OLP displays its antioxidant activity in vitro blocking the oxidation path that leads to methoxyl radicals hence to the formation of the stable radical species 5. The role of the catechol moiety was proved when the perferryl experiments were repeated in the presence of the dimethylated oleuropein homologue (OLP-Met2, 2). The dual behavior of oleuropein, similar to that ascertained for other catechol and non-catechol natural active species, should provide warnings for its use as nutraceutical or as drug with manifold healing effects.