Peroxide compounds are used both in laboratory and industrial processes for the electrophilic epoxidation of olefins. Using NMR-spectroscopy, we investigate why certain peroxides engage in this type of reaction while others require activation by metal catalysts, e.g. methyltrioxorhenium (MTO). More precisely, an analysis of ¹⁷O NMR chemical shift and quadrupolar coupling parameters provides insights into the relative energy of specific frontier molecular orbitals relevant for reactivity. For organic peroxides or H₂O₂ a large deshielding is indicative of an energetically high-lying lone-pair on oxygen in combination with a low-lying σ*(O–O) orbital. This feature is particularly pronounced in species that engage in electrophilic epoxidation, such as peracids or dimethyldioxirane (DMDO), and much less pronounced in unreactive peroxides such as H₂O₂ and ROOH, which can however be activated by transition-metal catalysts. In fact, for the proposed active peroxo species in MTO-catalyzed electrophilic epoxidation with H₂O₂ an analysis of the ¹⁷O NMR chemical shift highlights specific π- and δ-type orbital interactions between the so-called metal spectator oxo and the peroxo moieties that raise the energy of the high-lying lone-pair on oxygen, thus increasing the reactivity of the peroxo species.