The title polymeric complex of Cu(II) and Cd(II) bridged by thiocyanate, Cu(en)2[Cd(SCN)3]2, has been prepared and its structure determined by X-ray diffraction (XRD) methods. The crystal structure reveals that the Cu(II) atom is in an elongated octahedral coordination formed by two SCN anions and two en molecules. The Cd(II) atom is in a distorted octahedral coordination formed by six bridging SCN anions. Two different bridging thiocyanate anions exist in the complex. Both 1,1-μ-SCN and 1,3-μ-SCN anion act a role of bridge ligand and link Cu(II), Cd(II) atoms, and adjacent Cd(II). Cd(II) atoms form the three-dimensional (3-D) network polymeric structure. The IR and UV-Vis spectra have also been investigated.