Using the wire-arc additive manufacturing method (WAAM) on a 5083 aluminum alloy substrate, a non-equiatomic Mn – Cr – Fe – Co – Ni high-entropy alloy (HEA) coating was formed. By scanning and transmission electron diffraction microscopy we analyzed the structure, phase and elemental composition of the contact zone after irradiation with high-current low-energy electron beams with the following parameters: accelerated electron energy 18 keV, electron beam energy density 30 J/cm2, electron beam pulse duration 200 µs, number of pulses 3, pulse repetition rate 0.3 s–1. Multiphase multielement submicro- and nanocrystalline structures are formed predominantly in the substrate, which has a lower melting temperature compared to HEAs. Mutual doping of the coating – substrate system occurs in the contact layer, which has sinuous boundaries. The contact layers adjacent to the substrate and coating have the structure of high-speed cellular crystallization. In the layer adjacent to the substrate, the cells are formed by a solid solution of magnesium in aluminum. Interlayers of the second phase, enriched in atoms of the coating and substrate, are revealed along the cell boundaries. In the layer adjacent to the coating, the cells are formed by an alloy of composition 0.17Mg – 20.3Al – 4.3Cr – 16.7Fe – 9.3Co – 49.2Ni corresponding to the coating. Interlayers of the second phase, enriched mainly in magnesium and, to a lesser extent, in atoms of the HEA coating, are located along the cell boundaries. Central region of the contact zone with a thickness of ~1700 μm is formed by lamellar crystallites, which indicates the eutectic nature of its formation. Its main element is aluminum (≈77 at. %).