The selective catalysis of manganeseporphyrins for the aerobic oxidation of the different C-H bonds of methyl cyclohexane was reported. The effects of the peripheral substituents of metalloporphyrins and the reaction conditions on the catalytic selectivity were also investigated. It was found that manganeseporphyrins are effective catalysts for the aerobic oxidation of C-H bonds of methyl cyclohexane. The results showed that the increase of reaction temperature and pressure is benefited to selective oxidation of secondary C-H bonds, and the concentration of catalysts does not significantly influence the oxidation selectivity of every grade C-H bond. The electron-contributing substituents on porphyrin rings assist the selective oxidation of the secondary C-H bonds, while the electron-withdrawing substituents are favorable to selective oxidation of the tertiary C-H bonds. (c) 2005 Elsevier B.V. All rights reserved.