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Using the electron-ion-plasma additive method, a HEA film formed on a steel substrate (AISI 304) is saturated with boron by the PVD method from the gas-metal plasma formed by a simultaneous independent vacuum-arc discharge evaporation of the cathodes of selected elements in a plasma-assisted mode. Alloying of HEAs with boron, oxygen and substrate material atoms is revealed. It is shown that the multicycle modification of the HEA film is accompanied by the formation of a nanostructured multiphase layer with a thickness of 5–7 μm, containing inclusions of borides and oxides of the HEA chemical elements and those of the substrate. It is found out that the modification of the HEA film leads to a multiple (a factor of 18) decrease in its wear parameter.