Two novel organic-inorganic hybrid compounds based on Anderson-type polyoxoanions, [Cu-2(bpy)(2)(mu-ox)][Al(OH)(7)Mo6O17] (1) and [Cu-2(bpy)(2)(mu-ox)][Cr(OH)(7)Mo6O17] (2), have been synthesized and characterized by elemental analyses, IR, and X-ray powder diffraction. The crystal structures of 1 and 2 have been established by single-crystal X-ray diffraction, which reveals the presence of 1D chains constructed of alternating Anderson-type polyoxoanions and oxalato-bridged dinuclear copper complexes for both compounds and extensive hydrogen bonding that plays an important role in the formation of the 3D supramolecular network structures of 1 and 2. To elucidate the electronic properties and magnetic properties of the metal ions (Cu2+ or Cu2+ and Cr3+), EPR studies and magnetic susceptibility studies have been performed, respectively. The results are consistent with the structural feature of these compounds.