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A new three-dimensional (3D) lanthanide-aromatic monocarboxylate dimer supramolecular network [La2(DNBA)4(DMF)8][W6O19] (DNBA=3,5-dinitrobenzoate, DMF=dimethylfomamide) was synthesized using hexatungstate anion (W6O192-) as template. The crystal structure of the title compound has been determined by singlecrystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a=1.334 54(18) nm, b=1.387 52(19) nm,c=1.426 06(19) nm,α=102.189(2)°,β=101.023(2)°,γ=116.349(2)°,V=2.187 2(5) nm3,Dc=2.364 g·cm-3,Z=1,F(000)=1 453.40. The single crystal structure reveals that two La(Ⅲ) ions are bridged by four 3,5-dinitrobenzoate anions as asymmetrically bridging ligands, leading to dimeric cores, [La2(DNBA)4(DMF)8]2+; [La2(DNBA)4(DMF)8]2+ groups are joined together by π-π stacking interaction between the aromatic groups to form a two-dimensional grid-like network; the 2D supramolecular layers are further extended into 3D supramolecular network with a 1D box-like channels by hydrogen bonding interactions, in which hexatungstate polyanions reside. CCDC: 284694.