A novel organic-inorganic hybrid polyoxovanadate,[Ni(bpp)2]2(V4O12)(bpp=1,3-bi-4-pyridylpropane),was hydrothermally synthesized from a mixture of NiCl2·6H2O,NH4VO3,bpp,EtOH and H2O.The crystal structure consists of2∞[Ni(bpp)2+,two-dimensional networks interpenetrating perpendicularly with each other,and (V4O12)4-,cyclic tetranuclear clusters linking the 2∞[Ni(bpp)2]2+ networks to form a three-dimensional coordination framework.The crystal belongs to tetragonal space group I41/a with unit cell parameters,a=2.14705 nm,c=1.29293 nm.UV-Vis-NIR reflectance spectroscopy study revealed insulator nature for the crystal with an optical energy gap of 2.70 eV.