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A new compound, (H3O)3 {[Na3(H2O)13] [(Cu (Gly)2)2(H2W12O42)]}·11H2O (1), has been synthesized and structurally characterized, which represents the first example of a polyoxotungstate-surface being decorated with amino acid ligand. Two cis-{Cu(Gly)2}2+ engraft into the (H2W12O42)10- with Cu-O bond of 0.241 2(7) nm, and Na+ ions linked these [(Cu(Gly)2)2(H2W12O42)]6- clusters into a one-dimensional chain. CCDC: 278000.