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The crystal and molecular structures of the Na[Eu Ⅲ (edta) ( H2 O) 3] · 4H2O ( edta = ethylenediaminetetraacetic acid) and Na4[Eu2Ⅲ (Httha)2] · 10H2 O ( ttha = triethylenetetraminehexaacetic acid) complexes were determined by single-crystal X-ray structure analyses.The crystal of Na[ EuⅢ (edta) (H2O)3] · 4H2O belongs to orthorhombic crystal system and Fdd2 space group.The crystal data are as follows: a = 1.9415 (15)nm, b = 3.544(3 )nm, c = 1.203(9)nm, V = 8.327(5)nm3, Z = 16, M = 589.27, Dc= 1.880 g· cm-3, μ= 3.108mm-1 and F(000) = 4704.The final R and wR values are 0.0312 and 0.0750 for 2091[I ＞ 2.0σ (I)] reflections, and 0.0344and 0.0766 for all 3932 unique reflections, respectively.The[EuⅢ (edta) (H2O) 3] - anion has a nine-coordinate pseudo-monocapped square antiprismatic structure in which the nine coordinate atoms, two N and seven O, are from one edta ligand and three water molecules.The crystal of Na4[Eu2Ⅲ (Httha)2] · 10H2O belongs to orthorhombic system and Pccn space group.The crystal data are as follows: a = 2.610(3)nm, b = 2.089(3)nm, c = 2.239(3)nm, V =12.208 ( 28 ) nm3, Z = 8, M = 1548.92, Dc= 1.686g·cm-3,μ = 2.115 mm-1andF(000) = 6272.Thefinal R and wR are 0.0625 and 0.1091 for 9834[I ＞ 2.0σ(I)] reflections, and 0.1608 and 0.1471 for all 37818 unique reflections, respectively.The whole complex molecule is composed of two close parts in which each one has a nine-coordinate structure with distorted monocapped square antiprismatic prism.The ttha ligand in the[Eu2Ⅲ (Httha)2] 4- anion coordinates to one Eu Ⅲ ion with three N atoms and four O atoms and to the other Eu Ⅲ ion with two O atoms.