Metallic alloys can form multi-layer structures during the process of their synthesis. Such structures can be synthesized by direct components interaction, electrolytic deposition, magnetron sputtering, etc. The work to be presented describes the production of multi-phase structures of Al-Fe binary system in the result of two kinds of experiments of direct components interaction. First, the mechanochemical synthesis of alloys from the powders mixtures (Al+Fe) was carried out. Second, the direct interaction between solid Fe and liquid Al was performed. In spite of the methods difference, similar structures of alloys were obtained. Typically, the Al5Fe2 phase is formed as an intermetallic layer on the surface of Fe substrate or Fe powder particles. The core-shell structure is obtained in both the powder particles and Fe rods in a short time interval due to the intensive reactive diffusion of Al into Fe.