The entanglement density of amorphous glassy polymers is well known to control their fracture mechanisms under tensile loading. There have been some reports indicating substantial deformation of a glassy polymer’s surface region when exposed to interfacial friction. It is shown conclusively here that there is a direct correlation between the entanglement density of a glassy polymer and the deformation mechanisms that facilitate sliding friction. This correlation was shown experimentally by studying the topography of polymer surfaces following a single sliding pass by an inorganic glass sphere. Four different polymers were studied, including polystyrene cross linked to different degrees. It is also shown that permanent plastic deformation accompanies interfacial friction, and, furthermore, that the type of deformation is a direct function of the respective polymer’s entanglement density. In contrast, no difference in the observed friction force could be attributed to the entanglement density of the respective polymers. The findings can be explained by the state- and rate-dependent friction model.