The wear behavior of two kinds of high performance polymers, i.e. polyetheretherketone (PEEK) and Polybenzimidazole (PBI) was investigated at room and elevated temperatures (up to 175℃). After the wear tests, nanoindentation experiments were conducted to characterize the transfer film layer (TFL) on the steel couterface. The results showed that PBI possessed higher wear resistance when temperature is lower than 70℃, owing to its excellent thermal mechanical properties. However, PEEK showed lower wear rates at higher temperatures (> 150℃) because of the formation of the effective TFLs. It was also noticed that the brittle-ductile transition of polymers at high temperatures plays an important role in determining their wear performance.