Molecular simulations of the sliding processes of polymer-on-polymer systems were performed to investigate the surface and subsurface deformations and how these affect tribological characteristics of nanometer-scale polymer films. It is shown that a very severe deformation is localized to a band of material about 2.5 nm thick at the interface of the polymer surfaces. Outside of this band, the polymer films experience a uniform shear strain that reaches a finite steady-state value of close to 100%. Only after the polymer films have achieved this steady-state shear strain do the contacting surfaces of the films show significant relative slippage over each other. Because severe deformation is limited to a localized band much thinner than the polymeric films, the thickness of the deformation band is envisaged to be independent of the film thickness and hence frictional forces are expected to be independent of the thickness of the polymer films. A strong dependency of friction on interfacial adhesion, surface roughness, and the shear modulus of the sliding system was observed. Although the simulations showed that frictional forces increase linearly with contact pressure, adhesive forces contribute significantly to the overall friction and must therefore be accounted for in nanometer-scale friction. It is also shown that the coefficient of friction is lower for lower-density polymers as well as for polymers with higher molecular weights.