A new μ-chloro-bridged one-dimensional coordination polymer [Cd(dmbpy)Cl2]a (dmbpy = 4,4'-dimethyl-2,2'-bipyridine) has been synthesized and structurally characterized by elemental analyses, IR, UV spectra and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group C2/c with a = 17.745(4), b = 10.326(2), c = 7.3382(15)A, β = 106.85(3)°, V = 1286.9(4)A^3, Z = 4, C12H12N2Cl2Cd, Mr = 367.54, Dc = 1.897 g/cm^3, F(000) = 720, 2(MoKα) = 0.71073 A,μ= 2.089 mm^-1, R = 0.0368 and wR = 0.1048 for 1041 observed reflections (I 〉 2σ(I)). Cadmium(Ⅱ) adopts a distorted octahedral coordination geometry and adjacent coordination chains are intercalated in a zipper-like fashion into 2D layers through the π-π stacking interactions between dmbpy. Fluorescent analyses show that it exhibits intense blue photoluminescence in both DMF and DMSO solutions at room temperature.