The formation of transition metal complexes between dichlorocopper(II) and a poly(4-vinylpyridine)/divinylbenzene(2%) polymeric matrix is described in this contribution. The nitrogen atom of the pyridine groups of the organic polymer is coordinatively bonded to the Cu center as suggested by X-ray photoelectron spectroscopy (XPS), UV–vis/diffuse reflectance (UV–vis/DR), electron paramagnetic resonance (EPR), differential scanning calorimetry (DSC) and Fourier transform infrared (FT-IR) techniques. The immobilized catalyst was also characterized by DTA-TGA analysis and the morphology and elemental analysis of this copper/poly(4-vinylpyridine) complex were studied by the scanning electron microscopy/energy dispersive X-ray (SEM/EDX) technique. This material catalyzes the water gas shift reaction as well as the reduction of nitrobenzene to aniline and azobenzene.