Upon reaction of N‐substituted diethanolamines H2L2–4 (4, 6, 7) with cesium carbonate and bis(tetraethylammonium) tetrachloromanganate(II) in acetonitrile in the presence of air, the metal‐centered mixed‐valent manganese wheels NEt4{MnII⊂MnII3MnIII3Cl6(L2–4)6} (8–10) were generated. X‐ray crystallographic structure analyses revealed, that 8–10 are principally isostructural and consist of an alternating ring of three MnII and three MnIII ions, centered by an additional MnII ion. The cyclic voltammograms of 8 and 10 displayed three quasi‐reversible oxidation processes, which are attributed to the subsequent one electron‐oxidations of the three peripheral MnII ions to MnIII. Oxidation of the central MnII ion is not observed within the applied potential. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)