Water nucleophilic attack (WNA) on high-valent terminal Mn-oxo species is proposed for O–O bond formation in natural and artificial water oxidation. Herein, we report an electrocatalytic water oxidation reaction with MnIII tris­(pentafluorophenyl)­corrole (1) in propylene carbonate (PC). O2 was generated at the MnV/IV potential with hydroxide, but a more anodic potential was required to evolve O2 with only water. With a synthetic MnV(O) complex of 1, a second-order rate constant, k 2(OH–), of 7.4 × 103 M–1 s–1 was determined in the reaction of the MnV(O) complex of 1 with hydroxide, whereas its reaction with water occurred much more slowly with a k 2(H2O) value of 4.4 × 10–3 M–1 s–1. This large reactivity difference of MnV(O) with hydroxide and water is consistent with different electrocatalytic behaviors of 1 with these two substrates. Significantly, during the electrolysis of 1 with water, a MnIV-peroxo species was identified with various spectroscopic methods, including UV–vis, electron paramagnetic resonance, and infrared spectroscopy. Isotope-labeling experiments confirmed that both O atoms of this peroxo species are derived from water, suggesting the involvement of the WNA mechanism in water oxidation by a Mn complex. Density functional theory calculations suggested that the nucleophilic attack of hydroxide on MnV(O) and also WNA to 1e–-oxidized MnV(O) are feasibly involved in the catalytic cycles but that direct WNA to MnV(O) is not likely to be the main O–O bond formation pathway in the electrocatalytic water oxidation by 1.