Three inorganic organic hybrid compounds based on functionalized pentamolybdodiphosphonopropionate anion [(HO2CC2H4PO3)(2)Mo5O15](4-), [Co-3(bipy)(4)(H2O)(6){(HO2CC2H4PO3)(2)Mo5O15}(2)]center dot(H(2)bipy)(2)center dot 18H(2)O (1), [Fe-3(bipy)(4)(H2O)(6){(HO2CC2H4PO3)(2)Mo5O15}(2)]center dot(H(2)bipy)(2)center dot 18H(2)O (2), and [Cu(bipy)(H2O)(2){(HO2CC2H4PO3)(2)Mo5O15}]. (H(2)bipy)center dot 4H(2)O (3), where bipy = 4,4'-bipyridine, have been successfully synthesized at different pH values in aqueous solutions. In compound 1, [(HO2CC2H4PO3)(2)Mo5O15](4-) acts as a tridentate ligand and coordinates to the Co2+ ions of trimeric complexcations [Co-3(bipy)(4)(H2O)(6)](6+) forming a layer. In 3 [(HO2CC2H4PO3)(2)Mo5O15](4-) acts as a bidentate ligand and coordinates to the Cu2+ ions of complex chains [Cu(bipy)(H2O)(2)](n)(2n+), forming a different layer from that in 1. The three compounds were characterized by elemental analysis, IR spectra, and TGA. In addition, their fluorescent properties and magnetic properties have also been investigated.