Lacunary polyoxometalates represent a distinctive category of inorganic multidentate ligands that serve as precursors for building organic-inorganic hybrid materials and multinuclear metal oxo clusters. In this study, we successfully synthesized and characterized the organic-inorganic hybrid, [P2W12O44(C6H5PO3)2]10–. Two phenylphosphonato ligands were introduced at both ends of the vacant site to form the unique organic-inorganic-organic structure.