An iron complex with a tetraamido macrocyclic ligand, [(TAML)FeIII]-, was found to be an efficient and selective catalyst for allylic oxidation of cyclohexene by dioxygen (O2); cyclohex-2-enone was obtained as the major product along with cyclohexene oxide as the minor product. An iron(V)-oxo complex, [(TAML)FeV(O)]-, which was formed by activating O2 in the presence of cyclohexene, initiated the autoxidation of cyclohexene with O2 to produce cyclohexenyl hydroperoxide, which reacted with [(TAML)FeIII]- to produce [(TAML)FeV(O)]- by autocatalysis. Then, [(TAML)FeV(O)]- reacted rapidly with [(TAML)FeIII]- to produce a μ-oxo dimer, [(TAML)FeIV(O)FeIV(TAML)]2-, which was ultimately converted to [(TAML)FeV(O)]- when [(TAML)FeIII]- was not present in the reaction solution. An induction period was observed in the autocatalytic production of [(TAML)FeV(O)]-. The induction period was shortened with increasing catalytic amounts of [(TAML)FeV(O)]- and cyclohexenyl hydroperoxide, whereas the induction period was prolonged by adding catalytic amounts of a spin trapping reagent such as 5,5-dimethyl-1-pyrroline N-oxide (DMPO). The allylic oxidation of cycloalkenes was also found to depend on the allylic C-H bond dissociation energies, suggesting that the hydrogen atom abstraction from the allylic C-H bonds of cycloalkenes is the rate-determining radical chain initiation step. In this study, we have shown that an iron(III) complex with a tetraamido macrocyclic ligand is an efficient catalyst for the allylic oxidation of cyclohexene via an autocatalytic radical chain mechanism and that [(TAML)FeV(O)]- acts as a reactive intermediate for the selective oxygenation of cyclohexene with O2 to produce cyclohex-2-enone predominantly.