Complex studies of the formation of the superhard state in the TiZrHfNbTaYN vacuum-arc high-entropy coating were carried out. Based on the approach of the structural surface engineering, the regularities of the formation of the triads composition–structure–physico-mechanical properties depending on the supplied potential displacement are established. It is shown that the increase of U b at the formation of a coating leads to a decrease of the relative content of a light (Ti) and increase of a heavy (Ta, Hf) metal components, which is determined by radiationally stimulated processes in a near-surface region at the deposition. The formation of the single-phase state (based on the fcc of metal lattice) in the range U b from–50 to–250 V and revealed the formation of the preferred orientation of the crystallites with the axis [111], which is perpendicular to the growth plane. The increase of the perfection of the texture with the [111] axis with increasing U b is accompanied with an increase of the coatings hardness, which makes it possible to achieve the superhard state (H = 40.2 GPa) at U b =–250 V.