A novel coordination polymer [((VO)-O-IV)(2)(OH)(2)(C10H6(COO)(2))](infinity) based on vanadium(IV) and 2,6-naphthalenedicarboxylato ligand has been prepared by hydrothermal synthetic method. The compound was characterized by elemental analysis, thermogravimetric analysis, Fourier Transform infrared spectroscopy, room-temperature magnetic susceptibility measurement, manganometric titration, bond valance sum calculations (BVS), and single-crystal X-ray diffraction method. BVS calculations, manganometric titration, and room-temperature magnetic susceptibility measurement showed that the compound has paramagnetic property due to tetravalent vanadium ions. The single-crystal structure analysis of the compound illustrates a 2D metal organic framework structure. Coordination geometry of vanadium ions was a distorted square-pyramid (square-pyramidal coordination environment of oxygen atoms). The compound represents a novel 2D inorganic-organic coordination polymer involving vanadium(IV) and 2,6-naphthalenedicarboxylato ligand.