The title compound, {[Na(H(2)O)(4)](6)[V(10)O(28)]·2H(2)O}(n), crystallized from a H(2)O/THF/CH(3)CN solution (pH ca 6) containing equimolar amounts of NaVO(3) and N-(2-hydroxy-benz-yl)-N-(2-picol-yl)glycine. In the crystal structure, the deca-vanadate [V(10)O(28)](6-) anion ( symmetry) is coordinated, via four terminal oxide ligands of V centres, to two dinuclear [{Na(H(2)O)(3)}(2)(μ-H(2)O)(2)](2+) units. Inter-connection of these aquasodium-ion-sandwiched deca-vanadates to chains parallel to [001] is effected by μ-[{Na(H(2)O)(3)}(2)(μ-H(2)O)(2)](2+) units, bridging adjacent deca-vanadates via O=V. The structure is consolidated by an extensive network of O-H⋯O hydrogen bonds.