Analytical transmission electron microscopy has been applied to characterize the microstructure, phase and chemical composition of the Ag–Al wear track throughout its thickness down to the atomic level. Microscopy findings have been correlated with Ag–Al film tribological properties to understand the effect of the hexagonal solid solution phase on the tribological properties of this film. Ag–25Al (at.%) films have been produced by simultaneous magnetron sputtering of components in Ar atmosphere under 1 mTorr pressure and subjected to pin-on-disc tribological tests. It has been shown that hcp phase with (001) planes aligned parallel to the film surface dominates both in as-deposited and in tribofilm areas of the Ag–Al alloy film. Possible mechanisms of reduced friction in easily oxidized Ag–Al system are discussed and the mechanism based on readily shearing basal planes of the hcp phase is considered as the most probable one.