Results of studying the structural and physicomechanical properties of TiN/Cu coatings deposited from multicomponent separated vacuum-arc plasma are presented. Specific features of the formation of the nanostructured TiN-based coatings, which are alloyed with an element that does not form chemical compounds with titanium and nitrogen under the selected conditions of deposition, are considered. It is shown that alloying of the coating with this element leads to refinement of its structure. Regularities of variations in the microhardness and the tribological characteristics of TiN/Cu coatings of different elemental compositions are investigated. It has been found that the coatings that contain 2–4% of Cu have the highest microhardness (39–40 GPa) and the lowest coefficient of friction (0.2–0.4). Main factors responsible for the high wear resistance of the coatings are determined.