Nine ironporphyrins and eight manganeseporphyrins were synthesized, and their selective catalysis for the oxidation of the secondary and tertiary carbon-hydrogen bonds of 2-methyl-butane with PhIO was studied. The proportion of the oxidation product of tertiary carbon-hydrogen bond to the one of secondary carbon-hydrogen bond was 3:1 when ironporphyrins were used as catalysts, and 2.3:1 when manganeseporphyrins were used as catalysts. The research showed that the substituting groups on the porphyrin rings influenced the catalytic selectivity of metalloporphyrins for the oxidation of the secondary and tertiary carbon-hydrogen bonds as well as the reaction yields. The electron-attracting groups on benzene rings of ironporphyrins increased the catalytic selectivity of ironporphyrins for the tertiary carbon-hydrogen bond oxidation and the reaction speeds, and the electron-releasing groups increased the catalytic selectivity for secondary carbon-hydrogen bond oxidation and reduced the reaction speeds. Both electron-attracting and -releasing groups on benzene rings of manganeseporphyrins enhanced the catalytic selectivity of manganeseporphyrins for the secondary carbon-hydrogen bond oxidation.