Eight novel lanthanide-containing polyoxotantalates, Cs-3[Ln-(H2O)(6){H-4(TaO2)(6)As4O24}]center dot 7H(2)O (Ln = Sm (1), Eu (2), Tb (3), Dy (4), Er (5), Tm (6), Yb (7), Lu (8)), have been obtained via a one-pot reaction methodology. Each of these compounds is made up of the new type polyanion [(TaO2)(6)As4O24](10- )with Ln(3+) linkers, giving a one-dimensional chain. The compounds represent the first family of "pure" Ta-based polyoxometalate lanthanide derivatives. These architectures were characterized by various physicochemical analyses. Furthermore, the photoluminescence properties of compounds 2-Eu and 8-Lu were also explored, and meanwhile time-resolved emission spectroscopy indicated that the {As4Ta6} segment makes a contribution to the energy transfer of compound 2 from the polyoxotantalate to the Eu-III center, which efficiently facilitates emissions of the Eu3+ center.