A new metal-organic complex Cd2(cbba)4(phen)2 (Hcbba = 2-(4΄-chlorine-benzoyl)- benzoic acid, phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The compound crystallizes in orthorhombic, space group Pbcn with a = 12.0976(4), b = 18.0925(6), c = 31.6829(10) Å, V = 6934.6(4) Å3, C80H48Cd2Cl4N4O12, Mr = 1623.82, Dc = 1.555 g/cm3, μ(MoKα) = 0.8365 mm1, F(000) = 3264, Z = 4, the final R = 0.0396 and wR = 0.0960 for 5372 observed reflections (I > 2(I)). It exhibits a 3D supramolecular network through π-π interactions and shows green luminescent property at room temperature.