TiAl alloys (TAs) are widely used in aircraft and automotive industries, but their poor wear resistance restrains further applications. In this paper, the tribological properties of TiAl matrix self-lubricating composites containing lubricants of varying amounts (0.5 wt%, 1.5 wt% and 2.5 wt%) of V₂O₅ nanowires (NWs) and 5 wt% silver against Si₃N₄ balls were investigated from room temperature to 600 °C under the same conditions of 20 N load per bearing section and 0.35 m s⁻¹ gliding speed. TiAl–5Ag–1.5V₂O₅ NWs (TB) exhibited excellent tribological properties over a wide temperature range. Moreover, at 450 °C, TB showed a lower friction coefficient of 0.19 and a lower wear rate of 1.87 × 10⁻⁴ mm³ N⁻¹ m⁻¹, which were attributed to a continuous lubricating film containing V₂O₅ NWs and silver on the friction surface. Furthermore, in the formed lubricant films, silver was used as a solid lubricant to provide good lubrication, while V₂O₅ NWs played the role of a support with high shear strength. The investigation indicated that V₂O₅ NWs and silver exhibited an excellent synergistic effect for improving the tribological properties of TB.