A novel chemical approach is proposed to facilitate the crystallization of the BaTiO3 coating layer on Ni nanoparticles for multilayer ceramic capacitors. Based on the chemical equilibrium principle, the polycrystalline coating layer can be obtained at atmospheric pressure and at a relatively low temperature by a one-step reaction. The details of the coating process of the Ni nanoparticles are clearly discussed. The coating is uniform, dense, and well crystallized, and can protect the Ni from oxidation and also shift the starting point of Ni densification to a higher temperature, reducing differential shrinkage issues in the co-firing.