The reaction of CdCl2 with 6,7-dicyanodipyridoquinoxaline (DICNQ) by solvothermal reaction gives rise to a coordination polymer [CdCl2(DICNQ)]n 1. Single-crystal X-ray diffraction analysis reveals that the compound in space group Pbcn creates 1-D chloro-bridging chains. Crystal data for 1: a = 6.756(1), b = 35.371(6), c = 7.027(1) , V = 1679.1(5) 3, Z = 4.00, C16H6CdCl2N6, Mr = 465.57, Dc = 1.842 g/cm3, μ = 1.630 mm-1, F(000) = 904, S = 1.005 and T = 293(2) K. The final R = 0.0376 and wR = 0.1029 for 1291 observed reflections with I > 2σ(I), and R = 0.0499 and wR = 0.1125 for all data. The 1-D chloro-bridging chains are parallel-stacked in the a and b directions, and further stabilized through π-stacking interactions, hydrogen-bonding interactions and C≡N···π interactions to generate a 3-D structure. Compound 1 displays intense bluish-green photoluminescence from the intraligand charge-transfer of the DICNQ ligand and the Cl--to-DICNQ charge-transfer mechanism which is probed by the density of states (DOS) calculations. The reaction of CdCl2 with 6,7-dicyanodipyridoquinoxaline (DICNQ) by solvothermal reaction gives rise to a coordination polymer [CdCl2 (DICNQ)] n 1. Single-crystal X-ray diffraction analysis reveals that the compound in space group Pbcn creates 1- Crystal data for 1: a = 6.756 (1), b = 35.371 (6), c = 7.027 (1) , V = 1679.1 (5) 3, Z = 4.00, C16H6CdCl2N6, Mr = 465.57, Dc = 1.842 g / cm3, μ = 1.630 mm-1, F (000) = 904, S = 1.005 and T = 293 (2) K. The final R = 0.0376 and wR = 0.1029 for 1291 observed reflections with I > 2σ (I), and R = 0.0499 and wR = 0.1125 for all data. The 1-D chloro-bridging chains are parallel-stacked in the a and b directions, and further stabilized by π-stacking interactions, and C≡N ··· π interactions to generate a 3-D structure. Compound 1 displays intense bluish-green photoluminescence from the intraligand charge-transfer of the DICNQ ligand and the Cl-to-DICNQ charge-transfer mechanism which is p robed by the density of states (DOS) calculations.