An organic-inorganic polymer of [Nd(DMF)(6)(H2O)(2)][Nd(DMF)(6)(H2O)]P2W18O62 was synthesized by reaction of Nd2O3, DMF, HClO4 and alpha-H6P2W18O62 center dot nH(2)O in water and characterized by IR, UV, electrochemistry and single-crystal X-ray diffraction. The crystal of the title compound belongs monoclinic, space group Cc, with lattice constants: a=1.899 1(3) rim, b=2.204 7(3) nm, c=2.644 8(4) nm, beta=102.272(3)degrees, and Z=4, R-1=0.042 5, wR(2)=0.1045. The crystal structure reveals that Nd(1)(3+) complex ion is nine-coordinated with a tricapped trigonal prismatic environment, which is combined with the heteropolyanion by terminal oxygen atom, whereas Nd(2)(3+) complex ion is also nine -coordinated with a distorted monocapped square antiprismatic environment, which is linked to the heteropolyanion by terminal oxygen atom. Adjacent structure units of [{Nd(DMF)(6)(H2O)(2)}{Nd(DMF)(6)(H2O)}(P2W18O62)] are bridged through W-O-Nd(1)-O-W links to form one-dimensional linear chain. CCDC: 629927.