The effects of thermal oxidation of a biomedical titanium alloy (Ti–6Al–7Nb) on its morphology, structure, mechanical properties, and sliding friction and wear against alumina were investigated. It was found that at 600 °C, the surface of the alloy was characterized with a thin inhomogeneous oxide scale. Increasing the temperature of oxidation to 700 °C and 800 °C allowed obtaining homogeneous layers, which fully covered the examined surfaces. By contrast, the oxide scale obtained at 800 °C was composed of big oxide particles with a developed surface. Thermal oxidation process allows a fourfold increase in the hardness of Ti–6Al–7Nb alloy. It was shown that the oxide scale on the examined alloy efficiently enhances its resistance to sliding wear against alumina.