Three novel vanadogermanate cluster anions have been synthesized by hydrothermal reactions. The cluster anions are derived from the {V18O42} Keggin cluster shell by substitution of V=O2+ "caps" by Ge2O(OH)(2)(4+) species. in Cs-8[Ge4V16O42(OH)(4)].4.7H(2)O, 1, (monoclinic, space group C2/c (No. 15), Z = 8, a = 44.513(2) Angstrom, b = 12.7632(7) Angstrom, c = 22.923(1) Angstrom, beta = 101.376(1)degrees) and (pipH(2))(4)(pipH)(4)[Ge8V14O50.(H2O)] (pip = C4N2H10), 2 (tetragonal, space group P4(2)/nnm (No. 134), Z = 2, a = 14.9950(7) Angstrom, c = 18.408(1) Angstrom), two and four VO2+ caps are replaced, respectively, and each cluster anion encapsulates a water molecule. In K(5)HaGe(8)V(12)SO(52).10H(2)O, 3, (tetragonal, space group /4/m (No. 87), Z = 2, a = 15.573(1) Angstrom, c = 10.963(1) Angstrom), four VO2+ caps are replaced by GeO(OH)(2)(4+) species, and an additional two are omitted. The cluster ion in 3 contains a sulfate anion disordered over two positions. The cluster anions are analogous to the vanadoarsenate anions [V18-nAs2nO42(X)](m-) (X = SO3, SO4, Cl; n = 3, 4) previously reported.