Co(III) corroles were investigated as efficient catalysts for the reduction of dioxygen in the presence of perchloric acid in both heterogeneous and homogeneous systems. The investigated compounds are (5,10,15-tris(pentafluorophenyl)corrole)cobalt (TPFCor)Co, (10-pentafluorophenyl-5,15-dimesitylcorrole)cobalt (F(5)PhMeS(2)Cor)Co, and (5,10,15-trismesitylcorrole) cobalt (MeS(3)Cor)Co, all of which contain bulky substituents at the three meso positions of the corrole macrocycle. Cyclic voltammetry and rotating ring-disk electrode voltammetry were used to examine the catalytic activity of the compounds when adsorbed on the surface of a graphite electrode in the presence of 1.0 M perchloric acid, and this data is compared to results for the homogeneous catalytic reduction of O-2 in benzonitrile containing 10(-2) M HClO4. The corroles were also investigated as to their redox properties in nonaqueous media. A reversible one-electron oxidation occurs at E-1/2 values between 0.42 and 0.89 V versus SCE depending upon the solvent and number of fluorine substituents on the compounds, and this is followed by a second reversible one-electron abstraction at E-1/2 = 0.86 to 1.18 V in CH2Cl2, THF, or PhCN. Two reductions of each corrole are also observed in the three solvents. A linear relationship is observed between E-1/2 for oxidation or reduction and the number of electron-withdrawing fluorine groups on the compounds, and the magnitude of the substituent effect is compared to what is observed in the case of tetraphenylporphyrins containing meso-substituted C6F5 substituents. The electrochemically generated forms of the corrole can exist with Co(I), Co(II), or Co(IV) central metal ions, and the site of the electron-transfer in each oxidation or reduction of the initial Co(III) complex was examined by UV-vis spectroelectrochemistry. ESR characterization was also used to characterize singly oxidized (F(5)PhMeS(2)Cor)Co, which is unambiguously assigned as a Co(III) radical cation rather than the expected Co(IV) corrole with an unoxidized macrocyclic ring.