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The preparation and properties of the first heteropolyvanadates with transition metal central atoms and the first heteropoly anions with a 1:13 stoichiometry are reported. The complexes have been characterized by complete analysis of several salts, cryoscopy, magnetic susceptibility determination, and preliminary X-ray crystallographic examination. The salts K7(MnV13O38).18H2O and K7(NiV13O38).16H2O are isomorphous. Reduction of the manganate complex leads to an apparently isostructural mixed-valence anion (MnV12VO38)(8-). Although unstable in solution, the reduced species has been characterized by analysis and optical and esr spectroscopy. A proposed structure for the anion in K7(MnV13O38).18H2O, consistent with the observed unit cell symmetry, requires 39 oxygen atoms (one constitutional water molecule). Two new Mn(II) double salts, K2Mn2(V10O28).12H2O and K4Mn(V10O28).10H2O, have been proposed. (Author)