The stereoselectivity of olefin epoxidation catalyzed by Mn-III(salen)X (1a, X = Cl-; 1b, X = BF4-) complexes is examined in the presence of neutral donor ligands, employing various iodosylarenes (ArIO: PhIO, C6F5IO, and MesIO) as the oxygen atom source. The cis/trans ratios of stilbene oxides and the enantiomeric excesses of styrene oxide and 1,2-dihydronaphthalene oxide are found to be strongly dependent on the nature of the iodosylarenes under certain conditions. In other cases, olefin epoxidation is shown to proceed with essentially identical diastereoselectivities or enantioselectivities, regardless of the oxygen atom source used. We propose that a Mn-V(salen)-oxo intermediate and a complex between the catalyst and the terminal oxidant competitively effect the epoxidation when the stereoselectivities are markedly dependent on the oxygen atom source. A single Mn-V(salen)-oxo species is considered to be the sole oxygenating intermediate when the terminal oxidants do not exert a notable influence on the product selectivities. Our results clearly demonstrate the existence of multiple oxidizing species and the conditions in which only a single oxygenating intermediate is involved. The axial donor ligands (both anionic ligands and neutral ligands) are shown to strongly influence both the identity and the reactivity of the oxygenating species.