The tribological performance of two polymeric friction modifiers, one based on an ester‐based compound and another based on an ethoxylated fatty ester and an organic friction modifier, oleamide, was studied at 50, 90 and 140°C using a Mini Traction Machine equipped with optical interferometry and electrical contact resistance. The ability to form surface film is found to vary among the friction modifiers and with temperature and rubbing duration. Despite a thinner film being formed, polymeric friction modifier (PFMs) exhibited lower friction and wear than oleamide at all the studied temperatures. Further, the PFMs reduced boundary friction more effectively at higher temperature. In accordance with lower boundary friction, a smoother surface topography characterized by low wear was exhibited by PFM lubricated surfaces at higher temperatures. Scanning electron microscopy‐energy dispersive x‐ray analysis and time‐of‐flight secondary ion mass spectrometry provided insights on the tribofilm formation. The improvement in the tribological performance of PFMs is attributed to temperature‐induced conformation transition of adsorbed polymer chains on the surface. The results are corroborated by data obtained from dynamic light scattering and gel permeation chromatography.