The substructure of the surface layers of alitized nickel alloy is investigated. A layer-by-layer analysis was carried out. It is concluded that the alitized layer applied from the gaseous phase to a nickel substrate is characterized by different grain sizes and nonmonotonic residual stresses. The latter is controlled by the overall concentration of aluminum in the layer, and consequently by the activity of the alitizing process. It is also concluded that the relaxation of the internal stresses in the matrix sections of the substrate during aging proceeds on account of the development of the substructure of the alloy.