The oxoiron(IV) porphyrin pi-cation radical complex (compound I) has been identified as the key reactive intermediate of several heme enzymes and synthetic heme complexes. The redox properties of this reactive species are not yet well understood. Here, we report the results of a systematic study of the electrochemistry of oxoiron(IV) porphyrin pi-cation radical complexes with various porphyrin structures and axial ligands in organic solvents at low temperatures. The cyclic voltammogram of (TMP)(FeO)-O-IV, (TMP = 5,10,15,20-tetramesitylporphyrinate), exhibits two quasi-reversible redox waves at E-1/2 = 0.88 and 1.18 V vs SCE in dichloromethane at similar to 60 degrees C. Absorption spectral measurements for electrochemical oxidation at controlled potential clearly indicated that the first redox wave results from the (TMP)(FeO)-O-IV/[TMP+circle)(FeO)-O-IV](+) couple. The redox potential for the (TMP)(FeO)-O-IV/[(TMP+circle)(FeO)-O-IV](+) couple undergoes a positive shift upon coordination of an anionic axial ligand but a negative shift upon coordination of a neutral axial ligand (imidazole). The negative shifts of the redox potential for the imidazole complexes are contrary to their high oxygenation activity. On the other hand, the electron-withdrawing effect of the meso-substituent shifts the redox potential in a positive direction. Comparison of the, measured redox potentials and reaction rate constants for epoxidation of cyclooctene and demethylation of N,N-dimethylanilines enable us to discuss the details of the electron transfer process from substrates to the oxoiron(IV) porphyrin pi-cation radical complex in the oxygenation mechanisms.