The iron(III) complex [Fe-III(PMA)](ClO4)(2) (3) of a designed ligand PMAH (1; H is a dissociable amide H), which mimics the metal-binding domain of the antitumor antibiotic bleomycin, promotes alkane oxidation in conjunction with TBHP or H2O2. In anhydrous acetonitrile, reaction of 3 + TBHP with cyclohexane affords high yields of cyclohexanol and cyclohexanone (1:1 ratio, 1700% yield on the basis of catalyst concentration) along with the mixed peroxide (t)Bu-OO-Cy. The presence of water lowers the yields of oxidized products. Product ratios obtained in oxidations of adamantane and 3-methylpentane with 3 + TBHP confirm that reaction occurs at more-substituted carbon centers. No oxidation of an aromatic C-H bond is observed with 3 + TBHP. EPR spectra at low temperatures indicate that the low-spin Fe(III)-peroxo intermediate [(PMA)Fe-III-O-OR](+) (R = H, (t)Bu) is formed in the reaction mixture.