A new 3D extended structural compound,(dpdo)2H2{[Cu(2,2’-bipy)2]2(P2W18O62)}·5H2O 1(dpdo = 4,4’-bipyridine-N,N’-dioxide; 2,2’-bipy = 2,2’-bipyridine),has been hydrothermally synthesized and characterized by elemental analyses,IR,TG analyses,cyclic voltammetry,and single-crystal X-ray diffraction.Compound 1 is built up of[P2W18O62]6-cluster as the structural motif covalently linked by[Cu(2,2’-bipy)2]2+coordination complexes to yield the 1D chains,which are further in close contact forming a 3D supramolecular framework via aromaticπ-πstacking interactions and extensive hydrogen-bonding interactions among polyoxoanions,coordinated 2,2’-bipy organic ligands,free dpdo organic molecules and lattice water molecules.