In this study, the microstructure, high-temperature tribological performance, and mechanical properties of solution-aged Ti–10V–2Fe–3Al were investigated. The microstructure of solution-aged Ti–10V–2Fe–3Al reveals a bimodal α and β microstructure with uniformly dispersed α precipitates in the β matrix phase. The hot tribological performance of solution-aged Ti–10V–2Fe–3Al was investigated at different temperatures (28, 250, 350, and 450 °C) in a high-temperature pin-on-disc configuration. The wear mechanisms were evaluated at the worn-out surface using a scanning electron microscope (SEM). The abrasive wear mechanism is predominant at 28 °C and 250 °C testing conditions, whereas the oxidation and delamination are dominant wear mechanisms at 350 °C and 450 °C testing conditions. The worn-out surface at different temperature conditions was characterized by X-ray diffraction (XRD) and energy-dispersive X-ray spectrometer (EDS) analysis. The absence of protective oxide formation at 28 °C and intermittent protective oxide formation at 250 °C testing condition are ineffective in protecting the surface from wear damages and high wear loss. The protective tribo-oxide formations at 350 °C and 450 °C are continuous and provide improved wear resistance behavior of the material. The V2O5-rich tribo-oxide layer formation at 350 °C offers excellent wear resistance and protection against wear damages among the testing conditions. The Vickers microhardness study of the samples tested at different temperature conditions shows significant differences in the hardness magnitude at the cross section.