A family of isostructural 2D multinuclear LnIII-incorporated organic–inorganic hybrid arsenotungstates were fleetly synthesized, denoted as K4[{Ln(H2O)7}2 {As4W44O143(OH)8(H2O)6(DL-ala)2}{Ln2(H2O)4(DL-ala)}2]‧54H2O (Ln=Sm (1), Eu (2), Gd (3)), containing a centrosymmetric polyanion [{As4W44O143(OH)8(H2O)6(DL-ala)2}{Ln2(H2O)4(DL-ala)}2]8–. The polyanion is constituted of two {As2W19O62(OH)2(H2O)3}6– building blocks encapsulating a deca-nuclear Ln-W heterometallic cluster [W6O21(OH)4(DL-ala)2{Ln2(H2O)4(DL-ala)}2]6–. Obtained compounds were characterized by means of elemental chemical analysis, thermogravimetric, single crystal X-ray and powder diffraction and FT-IR studies. The optical band-gaps of 1 and 2 are 3.05 eV and 3.09 eV, respectively, according to the UV–Vis diffuse reflectance. In addition, 1 and 2 demonstrate the solid-state fluorescence performance (1: orange, 2: red), of which the POMs chromophore can be considered as an antenna ligand to improve luminescence efficiency of LnIII centers via energy migration.