A new 2D Ca(II) coordination polymer, [Ca(H(2)btc)(H2O)(2)](n) (1, H(4)btc = biphenyl-3,3',5,5'-tetracarboxylic acid), has been synthesized using the hydrothermal method and characterized by single-crystal X-ray diffraction, elemental analysis, IR, thermogravimetric analysis, and photoluminescent analysis. Complex 1 crystallizes in the monoclinic system, space group C2/c with a = 17.5676(15), b = 11.4496(8), c = 7.6197(8) angstrom, beta = 102.787(2)degrees, V = 1494.6(2) angstrom(3), Z = 4, D-c= 1.797 Mg.m(-3), mu = 0.483 mm(-1), F(000) = 832, the final R = 0.0348 and wR = 0.0915 for 1521 observed reflections with I > 2 sigma(I). Complex 1 has a 2D network containing 1D calcium-oxygen chains. These 2D networks are further connected by O-H center dot center dot center dot O hydrogen bonding interactions to generate a 3D supramolecular structure.