The present study is concerned with the influence of sputter-coatings CaO on the oxidation behavior of Ni polycrystals. The experiments were performed in air, in the temperature range 800°-1200°C. Below 1200°C, CaO coatings reduce the oxidation rate, while this beneficial effect disappears at 1200 °C. The oxidized specimens were examined by SEM and X-Ray diffraction, but also by EPMA depth profiling to evaluate the scale composition. Furthermore, electrical conductivity measurements and kinetic demixing studies were carried out on Ca-doped NiO single crystals, to get a better insight regarding the transport processes involved during oxidation. These last results show that the key features allowing to explain the effect of CaOcoatings on the oxidation rate of Ni are the influence of calcium on the increase of the dissociation pressure of NiO, which delays the oxidation of nickel, the kinetic demixing of the cations, which controls the distribution of CaO precipitates in the scale responsible for blocking effects, and the increase of the diffusion coefficient of both the cations and the cationic vacancies, which play a decisive role at high temperature, when the scale growth is dominated by lattice diffusion.