Three new extended frameworks built from paratungstate and transition metals have been synthesized and characterized. In thecompound Na8[{Cd (H2O)2}(H2W12O42)]10-32H2O (1), two neighboring paratungstate-B ions [H2W12O42]10- are linked by [Cd(H2O)2]2+units, leading to the formation of infinite one-dimensional (1D) anion chain [{Cd(H2O)2}(H2W12O42)]n8n-. The anion[{Co(H2O)3}{Co(H2O)4}(H2W12O42)]n6n-of the compound Na6[{Co(H2O)3}{Co(H2O)4}(H2W12O42)]- 29H2O (2) shows a layer-like(2D) structure in which paratungstate-B units are linked by CoO6 octahedra, while the anion [{Co(H2O)3}3(H2W12O42)]n4n-of thecompound (H3O+)3[{Na(H2O)4}{Co(H2O)4}3(H2W12O42)]- 24.5H2O (3) is a three-dimensional (3D) anionic polymer that consists ofparatungstate-B units linked by CoO6 octahedra. Compound 3 can reversibly adsorb and desorb water molecules leading to the colorreversibly change from pink to violet. The preliminary magnetic measurement and electrochemical properties of compounds areperformed. The crystal structure of unexpected product Na4[NiW6O24H6] _ 13H2O (4) is described here for the rare report of crystalstructure information on the Anderson-type polyoxotungstate which has nickel as a heteroatom.