The rate constants of the C═C epoxidation and the C–H hydroxylation (i.e., allylic C–H bond activation) in the oxidation of cyclohexene by a high-valent iron(IV)–oxo porphyrin π-cation radical complex, [(TMP^•+)Fe^IV(O)(Cl)] (1, TMP = meso-tetramesitylporphyrin dianion), were determined at various temperatures by analyzing the overall rate constants and the products obtained in the cyclohexene oxidation by 1, leading us to conclude that reaction pathway changes from the C═C epoxidation to C–H hydroxylation by decreasing reaction temperature. When cyclohexene was replaced by deuterated cyclohexene (cyclohexene-d₁₀), the epoxidation pathway dominated irrespective of the reaction temperature. The temperature dependence of the rate constant of the C–H hydroxylation pathway in the reactions of cyclohexene and cyclohexene-d₁₀ by 1 suggests that there is a significant tunneling effect on the hydrogen atom abstraction of allylic C–H bonds of cyclohexene by 1, leading us to propose that the tunneling effect is a determining factor for the switchover of the reaction pathway from the C═C epoxidation pathway to the C–H hydroxylation pathway by decreasing reaction temperature. By performing density functional theory (DFT) calculations, the reaction energy barriers of the C═C epoxidation and C–H bond activation reactions by 1 were found to be similar, supporting the notion that small environmental changes, such as the reaction temperature, can flip the preference for one reaction to another.