Three new tungsten(VI) oxide hybrid materials, [WO₃(pyz)_0.5] (pyz=pyrazine) 1, [WO₃(bpy)_0.5] (bpy = 4,4′-bipyridyl) 2 and [W₃O₁₀(enH₂)] 3, have been hydrothermally synthesized: 1 and 2 exhibit covalent/coordination hybrid framework connectivities while the structure of 3 consists of novel layers comprised of distorted {WO₆} octahedra linked through edge- and corner-sharing interactions.