A series of novel vanadium silicates with open-framework and microporous structures has been synthesized under mild hydrothermal conditions. Ten distinct framework types have been identified that all have structures based on cross-linking single silicate sheets with square pyramidal V(IV)O(5) units to give compounds with the general formula A(r)[(VO)(s)(Si(2)O(5))(p)(SiO(2))(q)].tH(2)O, where A is Na, K, Rb, Cs, or a combination. The vanadosilicate (VSH-n) structures have free channel diameters up to 6.5 A and show good thermal stability, absorption, and ion-exchange properties, suggesting their potential for technological applications as molecular sieves or in catalysis.