The title compound, tetrakis(tetraethylammonium) cyclo-tetra-micro-oxo-tetrakis[dioxovanadium(V)] dihydrate, (C(8)H(20)N)(4)[V(4)O(12)].2H(2)O, was obtained by reacting V(2)O(5) with (C(2)H(5))(4)NOH. It consists of a discrete centrosymmetric molecular anion, [V(4)O(12)](4-), where four tetrahedral VO(4) units share two vertices with each other to form a ring. A water molecule is attached on each side of the ring through hydrogen bonds.