The effect of axial ligand on the reactivity of oxomanganese(V) 5,10,15-tris(pentafluorophenyl)corrole (tpfc)(MnO)-O-v had been investigated by kinetic method. It was found the reactivity of (tpfc)(MnO)-O-v towards styrene could be greatly enhanced by axial coordination interaction. Catalytic experiments indicated that the turnover frequency (TOF) of (tpfc)Mn-III-catalyzed epoxidation of styrene with PhIO was increased about 7 times in the presence of imidazole (catalyst/ligand, 1:10). Theoretical calculations showed that axial coordination will lower the binding energy of Mn=O bond in (tpfc)(MnO)-O-v.