An alkaline earth metal-organic framework [Ba(Hsip)(H2O)4]n (1, NaH2sip = 5-sulfoisophthalic acid sodium) has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba(II) atom coordinates to one ligand Hsip3- and four water molecules with a distorted nine-coordinated monocapped tetragonal antiprism geometry. Each Hsip2- anion acts as a μ3-bridging ligand, in which two carboxylate groups adopt the same bidentate chelating coordinating model and the sulfonate group takes a monodentate coordinating model, resulting in a wave-like two-dimensional network with a (6, 3) topological structure. The two-dimensional networks are further linked by O-H···O to form a three-dimensional structure. Luminescent property and thermal stability of complex 1 are investigated. 1 belongs to the orthorhombic system, space group Pna21 with a = 7.3333(2), b = 16.7044(3), c = 10.4817(2), Z = 4, V = 1283.99(5)3, Mr = 453.58, Dc = 2.346 g/cm3, F(000) = 880, μ = 3.314 mm-1, the final R = 0.0261 and wR = 0.0592 for 2425 observed reflections with I > 2σ(I). In complex 1, each Ba (Hsip) (H2O) 4] n (1, NaH2sip = 5-sulfoisophthalic acid sodium) has been constructed and characterized by single-crystal X-ray diffraction (II) atom coordinates to one ligand Hsip3- and four water molecules with a distorted nine-coordinated monocapped tetragonal antiprism geometry. Each Hsip2-anion acts as a μ3-bridging ligand, in which two carboxylate groups adopt the same bidentate chelating coordinating model and the sulfonate group takes a monodentate coordinating model, resulting in a wave-like two-dimensional network with a (6, 3) topological structure. The two-dimensional networks are further linked by OH ··· O to form a three-dimensional structure . 1 belongs to the orthorhombic system, space group Pna21 with a = 7.3333 (2), b = 16.7044 (3), c = 10.4817 = 1283.99 (5) 3, Mr = 453.58, Dc = 2.346 g / cm3, F (000) = 880, μ = 3.31 4 mm-1, the final R = 0.0261 and wR = 0.0592 for 2425 observed reflections with I> 2σ (I).