Abstract: The electrochemistry of [Cu(OEP)] and [Ni(OEP)] are compared with the mixed-valence π-cations [Cu(OEP•/2)]2+and[Ni(OEP•/2)]2+. These electrochemical studies, carried out with cyclic voltametry and hydrodynamic voltametry, show that the mixed valence π-cations have distinct electrochemical properties, although the differences between the [M(OEP)](+/0) and [M(OEP•/2)]2+/0 processes are subtle.