Two novel transition metal phosphonate compounds,[Co(H2BDPP)(phen)]n 1 (BDPP = p-O3PCH2(C6H4)CH2PO3,phen = 1,10-phenanthroline) and [Pb3(BCP)2]n 2 (BCP = OOC(C6H4)CH2PO3),have been synthesized and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in the monoclinic system,space group C2/c with a = 21.169(4),b = 12.001(2),c = 7.6211(15) ,β = 98.03(3)o,V = 1917.2(6) 3,C20H18N2O6P2Co,Mr = 505.22,Z = 8,Dc = 1.737 g/cm3,μ = 1.107 mm-1,F(000) = 1020,the final R = 0.0450 and wR = 0.1306 for 2072 observed reflections (Ⅰ > 2σ(Ⅰ)). Compound 2 crystallizes in the monoclinic system,space group C2/c with a = 4.7167(9),b = 18.753(2),c = 22.781(3) ,β = 91.07(3)o,V = 2014.7(14) 3,C8H6O5PPb1.5,Mr = 523.88,Z = 8,Dc = 3.454 g/cm3,μ = 25.222 mm-1,F(000) = 1856,the final R = 0.0441 and wR = 0.1906 for 2259 observed reflections (Ⅰ > 2σ(Ⅰ)). In compound 1,the 1D chain running along the c axis is bridged by four ligands (trans-HO3PCH2C6H4CH2PO3H) in four different directions to extend the structure into a threedimensional network. In compound 2,the Pb(Ⅱ) displays 4-and 5-coordination modes. There is a one-dimensional P-O-Pb band along the a axis formed by PO3 groups and Pb(Ⅱ) cations. These bands are joined by μ2-O of-COO to yield two-dimensional inorganic P-O-Pb layers which are pillared by the OOCC6H4CH2PO3 ligands to form a three-dimensional network. Moreover,compound 2 displays a strong emission band attributed to the ligand-centered (LC) transition.