The synthesis and X-ray structure determination of the first polyoxoeuropioniobate complex, {[Eu3O(OH)(3)(OH2)(3)]Al-2(2)(Nb6O19)(5)}(26-) (1), is reported. 1 has D-3 point symmetry and is comprised of two trimeric oxohydroxoaquoeuropium clusters, five hexaniobate anions and two Al3+ cations. Each [Eu3O(OH)(3)(OH2)(3)](4+) core is linked to an axial [Nb6O19](8-) anion via an Al3+ cation and is also connected to the other Eu-3 core through the three equatorial [Nb6O19](8-) anions.