The addition of an organic acid to the manganese­(V)-oxo corrole complex (tpfc)­MnV(O) (tpfc = 5,10,15-tris­(pentafluorophenyl)­corrole) induces valence tautomerization resulting in the formation of (tpfc+•)­MnIV(OH) in acetonitrile at 298 K. The corrole radical cation manganese­(IV) hydroxo complex has been fully characterized by EPR, 1H NMR, and UV–vis spectroscopy. The reactivity of the valence tautomer (tpfc+•)­MnIV(OH) is compared to that of (tpfc)­MnV(O) in three reaction types: hydrogen atom transfer (HAT), electron transfer (ET), and oxygen atom transfer (OAT). (tpfc+•)­MnIV(OH) shows a dramatic 5 orders of magnitude enhancement in the rate of ET but surprisingly does not undergo OAT with PhSMe. The high-valent (tpfc)­MnV(O) complex is moderately more reactive toward HAT with substituted phenol and shows superior activity in OAT.