To promote the optimization of the anti-friction and anti-wear behavior of lightweight TiAl alloys, γ-TiAl-10 wt.% Ag self-lubricating composites were fabricated, and their mechanical and tribological properties were tested. The results showed that the silver in TiAl-10 wt.% Ag slightly reduced its mechanical properties compared with those of pure TiAl alloys. A silver-enriched lubrication film formed on a wear scar, which was helpful in improving the friction and wear behavior. It was found that a large amount of silver gathered at a wear scar, gradually spread out under the action of the sliding friction force, and then increased the silver distribution areas on the wear scar, leading to the good formation of a silver-rich film. Furthermore, an identification model was established to calculate the specific area η of the silver film. A quantitative relationship indicated that an increase in the Ag distribution area improved the tribological behavior of γ-TiAl-10 wt.% Ag. When the specific area η of a silver-rich film was maintained at 44–51%, the small friction coefficient (almost 0.28) and wear rate (about 2.25 × 10−4 mm3·N−1·m−1) were well stabilized. This provides a new research method to improve the tribological performance of TiAl-Ag samples.