The paper presents the optimization process for obtaining NiO thin layers on copper substrate for solar absorber coatings, using an inexpensive and up-scalable technique: spray pyrolysis deposition (SPD). Efficient selective coatings must present a high absorption coefficient of the incident solar irradiation, and low emission of heat. The solar selective coatings design involves tailoring the surface properties for superior optical properties. The deposition parameters were varied for maximizing the solar absorbance and minimizing the thermal emittance. The film morphology was controlled using copolymers of the maleic anhydride as additives into the precursors' solution. The structural and surface properties of the films were investigated by X-ray diffraction and atomic force microscopy, respectively. The Cu/CuO(x)/NiO solar absorber shows good values for the solar absorptance (alpha(s) = 0.95) and thermal emittance (epsilon(T) = 0.05) compared with the ones obtained by other methods employed in literature and new additives are recommended in tailoring the surface of solar selective coatings.