A new coordination polymer {[Ba(L)(H2O)(5)]center dot H2O}(n) (1, H2L = 3,3'-((((ethane-1,2-diylbis(oxy))-bis(2,1-phenylene))bis(methylene))bis(oxy))dibenzoic acid) has been synthesized under evaporation process and characterized by elemental analysis, IR spectra, TG analysis, fluorescence spectrum, powder X-ray diffraction analysis and single-crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic system, space group P2(1)/c, with a = 20.918(5), b = 7.4539(2), c= 20.168(5) angstrom, beta = 95.486(2)degrees, V = 3130.1(1) angstrom(3), Z= 4, C30H34BaO14, = 755.91;D-c = 1.604 g/cm(3), F(000) = 1528, mu = 1.34 mm(-1), the final R = 0.0404 and wR = 0.0676 for all data. Single-crystal X-ray structural reveals that the Ba(II) ion adopts a nine-coordinated distorted tricapped trigonal prism coordination geometry. Adjacent Ba(II) ions are linked by one mu(2)-L2- anion and two (mu(2)-H2O) water molecules to generate an infinite 1D zigzag chain structure. Then these chains are further linked into a 2D layer supramolecular architecture through O-H center dot center dot center dot O hydrogen bonds. Luminescent property and thermal stability of complex 1 were investigated.