Three types of heteropolyvanadates, [(C2H5)(4)N](4)[PdV6O18] (1), [(C2H5)(4)N](4)[Cu2V8O24] (2), and [(C6H5)(4)P](4)[Ni4V10O30-(OH)(2)(H2O)(6)] (3), were synthesized through the reaction between the NOT anion and metal template cations of Pd(II), Cu(II), and Ni(II). The X-ray crystal structures of 1 (a = 29.952(4) A, b = 12.911(2) A, and c = 13.678(2) A, orthorhombic, space group Pca2(1) with Z = 4), 2 (a 13.740(1) angstrom, b = 22.488(2) angstrom, c 18.505(2) angstrom, and beta = 94.058(2)degrees, monoclinic, space group P2(1)/n with Z = 4), and 3 (a = 12.333(2) angstrom, b 16.208(4) angstrom, c = 16.516(3) angstrom, alpha = 112.438(3)degrees, beta = 94.735(3)degrees, and gamma = 104.749(3)degrees, triclinic, space group P1 with Z = 1) demonstrate that the metal cationic species induced Cyclic [VO3](n)(n-) (n = 6, 8, 10) ring formation and the cations are incorporated in the rings themselves. In the metal inclusion products, the cyclic vanadates act as macrocyclic ligands, in which the metal cationic species act as the templates. The cyclic vanadate is composed of tetrahedral VO4 units that share corners and incorporates a metal cationic species in the center of the molecules. The bowl-shaped complex 1 includes a Pd2+ cation that is coordinated by the oxygen donors of a boatlike hexavanadate ring. The diamagnetic complex 1 was characterized via V-51 and O-17 NMR spectroscopy. Complex 2 involves an octavanadate ring and two Cu2+, which are located on both sides of the mean plane as defined by the eight oxygen atoms that bridge the vanadium atoms. In the case of complex 3, the di-,mu-hydroxo-bridged Ni2+ dimer with capped Ni2+ aqua ions is formed by hydrolysis to form the decavanadate ring, in which two of the tetrahedral vanadate units are not bonded to the Ni2+ core but supported by hydrogen bonds through the aqua-ligand in the capped Ni2+ cation. Complexes 1-3 in solution were clearly identified by their characteristic isotope patterns using ESI-MS studies.