The reproducibility of the single-phase structural state of the Ti-V-Zr-Nb-Hf multielement system (a high-entropy alloy) is demonstrated using the vacuum-arc method to prepare coatings based on this system. Single-phase high-entropy compounds with a bcc lattice typical of the molten state result from vacuum deposition; preparation in nitrogen atmosphere yields single-phases nitride superhard nanocrystalline coatings based on the fcc metallic lattice.