AbstractA bisupporting Keggin-type polyoxometalate compound, {[CuII(phen)2]2[(HBW12O40)]}[CuIICl2(phen)]2· 2H2O (phen=1,10-phenathroline) (1), has been synthesized through the hydrothermal method and characterized by IR spectroscopy, elemental analysis, UV/Vis/NIR spectroscopy, and powder and single crystal X-ray diffraction. The bisupporting Keggin-polyoxometalate consists of one Keggin-type [HBW12O40]4−core and two covalently linked copper(II) complex fragments [Cu(phen)2]2+. In the crystal structure π···π interactions, C–H···Cl, O–H···Cl, O–H···O and C–H···O hydrogen bonds lead to a three-dimensional supramolecular structure.