The N-confused porphyrin complex Mn-II(NCHPP)Br exhibits a nonplanar porphyrin ring with an inner core C-H on the inverted pyrrole ring. The aerobic metal oxidation promotes the dissociation of an inner-core proton on the inverted pyrrole ring and changes the N-confused porphyrin conformation to a planar porphyrin ring to form Mn-III(NCPP)Br. The conjugate systems and metal oxidation states are confirmed by crystal structures as well as spectroscopic data. The reverse reaction can be achieved by treating the Mn-III(NCPP)Br with p-toluenesulfonhydrazide.