Localized valencies are displayed by the Mn(V)-Mn(II) complex ion 1. This is the key finding from X-ray structure analysis, as well as vibrational and EPR spectroscopic invesigations on 1 obtained by the reaction of manganese(II) and [Mn(v)(N)(CN)(5)](3-) salts in aqueous 1 M NaCN solution. Remarkably, the asymmetry is induced by the nitrogen atom bridge.