By using a flexible multidentate ligand,bis(2-hydroxyethyl)iminotris(hydroxyhydroxylmethy)methane('bis-tris':H5L),the title complex {[Na(H6L)2]2}n·nV10O28(1) has been successfully synthesized under self-assembly condition and characterized by IR spectroscopy,elemental analysis,PXRD and single-crystal X-ray diffraction.The crystal structure belongs to an orthorhombic system,space group Cmca with a = 23.752(2),b = 13.5360(8),c = 18.5377(11) ,V = 5960.1(7),Z = 8,Dc = 2.055 g/cm3,F(000) = 3744,μ = 1.630 mm-1,the final R = 0.0283 and wR = 0.0759 for 3353 observed reflections with I 〉 2σ(I).This complex consists of decavanadate [V10O28]6-motifs as counter anions intercalated with one-dimensiond chains of the composition [Na(H6L)2]n3n+.And significant intermolecular O-H…O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework.