The mechanisms of heterolytic versus homolytic O-O bond cleavage of H2O2, tert-butyl hydroperoxide (t-BuOOH), 2-methyl-1-phenyl-2-propyl hydroperoxide (MPPH), and m-chloroperoxybenzoic acid (m-CPBA) by iron(III) porphyrin complexes have been studied by carrying out catalytic epoxidations of cyclohexene in protic solvent. In these reactions, various iron(III) porphyrin complexes containing electron-withdrawing and -donating substituents on phenyl groups at the meso position of the porphyrin ring were employed to study the electronic effect of porphyrin ligands on the heterolytic versus homolytic O-O bond cleavage of the hydroperoxides. In addition, various imidazoles were introduced as axial ligands to investigate the electronic effect of axial ligands on the pathways of hydroperoxide O-O bond cleavage. Unlike the previous suggestions by Traylor, Bruice, and co-workers, the hydroperoxide O-O bonds were found to be cleaved both heterolytically and homolytically and partitioning between heterolysis and homolysis was significantly affected by the electronic nature of the iron porphyrin complexes (i.e., electronic properties of porphyrin and axial ligands). Electron-deficient iron porphyrin complexes show a tendency to cleave the hydroperoxide O-O bonds heterolytically, whereas electron-rich iron porphyrin complexes cleave the hydroperoxide O-O bonds homolytically. The heterolytic versus homolytic O-O bond cleavage of the hydroperoxides was also found to be significantly affected by the substituent of the hydroperoxides, ROOH (R = C(O)R', H, C(CH3)3, and C(CH3)2CH2Ph for m-CPBA, H2O2, t-BuOOH, and MPPH, respectively), in which the tendency of O-O bond heterolysis was in the order of m-CPBA > H2O2 > t-BuOOH > MPPH. This result indicates that the O-O bond of hydroperoxides containing electron-donating tert-alkyl groups such as t-BuOOH and MPPH tends to be cleaved homolytically, whereas electron-withdrawing substituents such as an acyl group in m-CPBA facilitates O-O bond heterolysis. Since we have observed that the homolytic O-O bond cleavage of hydroperoxides prevails in the reactions performed with electron-rich iron porphyrin complexes and with hydroperoxides containing electron-donating substituents such as the tert-alkyl group, we suggest that the homolytic O-O bond cleavage is facilitated when more electron density resides on the O-O bond of (Porp)Fe(III)-OOR intermediates. We also present convincing evidence that the previous assertion that the reactions of iron(III) porphyrin complexes with hydrogen peroxide and tert-alkyl hydroperoxides invariably proceed by heterolytic O-O bond cleavage in protic solvent and that the failure to obtain high epoxide yields in iron porphyrin complex-catalyzed epoxidation of olefins by hydroperoxides is due to the mechanism of heterolytic O-O bond cleavage followed by a fast hydroperoxide oxidation is highly unlike.