Rate constants of electron self-exchange of high-valent oxo and imido complexes of chromium­(V/IV) corrole have been determined in acetonitrile and toluene at various temperatures by electron paramagnetic resonance (EPR) line width variation of the EPR spectra. The observed activation enthalpies (ΔH obs ⧧) of electron self-exchange of chromium­(V)–oxo and –imido corrole with the corresponding chromium­(IV) complexes are zero in toluene, whereas the ΔH obs ⧧ values are slightly positive in acetonitrile. Such activationless electron self-exchange transfer resulted in extremely fast electron-transfer reactions of chromium­(V)–oxo and −imido corrole in sharp contrast with slow electron-transfer reactions of other high-valent metal–oxo and −imido complexes.