A novel organic–inorganic coordination polymer [CdCl 3(CH 3) 3NH] 1 was synthesized by the reaction of CdCl 2 with trimethylamine (TMA) at 170 °C for 5 days in ethanol and structurally characterized by means of X-ray single diffraction. The title compound affords a one-dimensional chain structure. It crystallizes in hexagonal system space group P 6 ( 3 ) / m with a = 9.1401 ( 13 ) Å , b = 9.1401 ( 13 ) Å , c = 6.7313 ( 13 ) Å , γ = 120.00 ° , V = 487.00 ( 14 ) Å 3 , Z = 2 , D C = 1.895 Mg / m 3 , F ( 000 ) = 266 , M r = 277.86 , μ ( Mo K α ) = 2.99 mm −1 , the final R = 0.0420 and ω R = 0.1020 for 355 observed reflections with I > 2 σ ( I ) . The title compound consists of cation [(CH 3) 3NH] + and anion chain [ ( CdCl 3 ) ] n − , and they are combined by static attracting forces in the crystal. TG–DTA, XRD and IR data for the title compound are reported and discussed. The photoluminescent properties of the compound 1 were also investigated.