Photochemical deposition of copper nanoparticles onto polystyrene surface under monochromatic (λ 254 nm) and unfiltered irradiation was studied. The kinetic parameters of this process depending on the concentration of copper(II) coordination compound and the size of polystyrene microspheres were determined. A procedure was tested for the preparation of monodisperse copper nanoparticles from colloidal copper chemically synthesized in ethylene glycol matrix in the presence of polystyrene with a microsphere size of 100 nm.