We present two new-routes to synthesize [(MnMnIV)-Mn-III(O)(2)(phen)(4)](ClO4)(3) (1, phen = 1,10-phenanthroline). The crystal structure of 1 shows structurally distinct Mn ions with a Jahn-Teller distorted Mn-III and an undistorted Mn-IV, indicating an electron-localized complex; the 16-line EPR signal from 1 also shows that this is a trapped-valences complex.