Novel mixed-metal Cu(I)-Ni(Ⅱ) coordination polymers having an infinite one-dimensional (1D) structure, {[CuI5NiIⅡ5(Pip-dtc)2(C2H5CN)]・CHCl3}n (1) and {[CuI5CuⅡI5(Hm-dtc)2(C2H5CN)]・CHCl3}n (2) (Pip-dtc- = piperidine dithiocarbamate and Hm-dtc- = hexamethylene dithiocarbamate), have been prepared and structurally characterized via X-ray diffraction. These complexes comprised a mononuclear Ni(Ⅱ) unit, CuⅡL2, and a pentanuclear Cu(I) cluster unit, CuI5I5(C2H5CN)2. The energy states of these coordination polymers were investigated via photoelectron spectroscopy and diffuse reflectance spectroscopy, which indicated the formation of the narrow bands based on the weak orbital's overlap between the mononuclear Ni(Ⅱ) unit and the pentanuclear Cu(I) cluster unit.