Treatment of vanadium(V) oxide with an ethanol-concentrated sulfuric acid mixture, followed by the addition of an equimolar amount of beta-alanine and sodium hydroxide, and finally raising the pH to 3.9 with sodium carbonate solution, under continuous heating in a water bath and in the presence of air, leads to the polyionic sodium cyclo -{mu(6)- (sulfato-0,O',O") tris [mu-(beta-alanine-O,O') -mu -oxo] - tris(mu-hydroxo-mu-oxo)hexa[oxovanadium(V)]} sulfate tridecahydrate which crystallizes in the monoclinic P2(1)/n space group [a = 9.5192-(4), b = 20.1185(9), c = 22.6174(9) Angstrom, beta = 97.011 (1)degrees; Z = 4]. The crown-shaped polyoxovanadium(V) cluster cation, with carboxylate-bridging amino acid ligands, has an Anderson structure with two unique capping sulfato ligands. Its structural analysis, together with IR, UV-vis, and preliminary data on its solution properties, is presented.