Abstract <p>This paper investigates the tribological behavior and evolution of the structural–phase state of the surface of additively manufactured hypereutectoid Ti6Al4V–Cu alloys with copper contents of 15, 19, and 25&#xa0;wt % after dry sliding against steel. The alloys were produced using twin-wire electron beam additive manufacturing. It was established that the addition of 15 and 19 wt % Cu promotes the formation of fully equiaxed grains, while the microstructure consists of α(α')-Ti and a secondary eutectoid Ti₂Cu needle-like structure. This microstructural design enhances the wear resistance of Ti6Al4V–15Cu and Ti6Al4V–19Cu alloys by 50 and 43%, respectively, compared to additively manufactured Ti6Al4V. In contrast, the addition of 25 wt % Cu results in the formation of coarse primary Ti₂Cu grains, which leads to increased wear rate and friction coefficient in the Ti6Al4V–25Cu alloy. Nevertheless, catastrophic brittle fracture of the samples was not observed. The formation of a tribological layer composed of alloy oxides and counterbody particles facilitated tribological adaptation and reduced the overall wear of Ti6Al4V–Cu alloys. Consequently, the contribution of the adhesive wear mechanism to the total wear of the titanium alloy was reduced due to the development of composite-like materials based on hypereutectoid Ti6Al4V–Cu alloys, associated with the formation of intermetallic compounds.</p>