Three new organic-inorganic hybrid lanthanide-substituted organophosphonate-based polyoxomolybdates (NH4)2Na3.5H1.5 [{Nd(H2O)7}3{Mo5O15 (1,4-O3PCH2C6H4CH2PO3)}4]·41H2O (2) (NH4)5NaH13 [{Nd(H2O)3}{Nd(H2O)4}{Nd(H2O)7}3{Mo5O15(1,4-O3PCH2C6H4C H2PO3)}8]·Cl2·55H2O (3) and (NH4)3Na2H2 [{Nd(H2O)7}{Nd(H2O)6}2{Mo5O15(1,4-O3PCH2C6H4CH2PO3)}4]·38H2O (4) have been successfully synthesized and characterized by single crystal X-ray diffraction, elemental analysis, PXRD and IR spectra, etc. The square-ringed anion of (NH4)2Na12H2 [{Mo5O15(1,4-O3PCH2C6H4CH2PO3)}4]·28H2O (1)is formed via four {Mo5O15} units, linked together via four organophosphine ligands 1, 4-H2O3PCH2C6H4CH2PO3H2 sequentially. Three examples of Ln-containing organophosphonate-functionalized polyoxomolybdates derivatives 2−4 were obtained by changing the pH through adding rare earth ions. Compounds 2−4 are linked to Nd3+ on the basis of compound 1. Interestingly, five Nd 3+ were connected to compound 3 when the pH was adjusted to 2.20 and the number of Nd 3+ decreased to three with the increasement of the pH value of the reaction system. Their special structural feature are tetrameric ring-shaped structures consisting of four [Mo5O15(1,4-O3PCH2C6H4CH2PO3)]4− segment stabilized by two [Ln (H2O)7]3+ cations, which is connected by Nd3+ ions into a one-dimensional mesh structure form. The luminescence characteristics of solid samples 2−4 at room temperature are studied. The fluorescence test results show that compounds 2−4 exhibit characteristic emission of rare earth ions.