Tribological properties of thermosetting polyimide (TPI) mated with Si 3 N 4 , Al 2 O 3 and GCR15 balls are investigated from room temperature to 300℃. TPI mated with ceramic balls, shows lower coefficient of friction (COF) and wear rate (WR) under room temperature, due to the inexistence of transfer film on TPI-ceramic balls, which is demonstrated by Energy Dispersive Spectrometer (EDS) and different wear mechanisms. And a conclusion is drawn that transfer film can hardly form on ceramic balls due to the low chemical activities of ceramic materials, Downloaded by [UQ Library] at 02:48 13 July 2015 ACCEPTED MANUSCRIPT ACCEPTED MANUSCRIPT 2 especially under higher load conditions. Under high temperatures, COFs of TPI-ceramic balls present diverse trend compared to TPI-GCR15. Moreover, transfer films on ceramic balls begin to form as the temperature rising, which is easily determined by EDS of tribological marks on ceramic balls. The differences presented above mainly can be ascribed to the diversities of different properties of mated balls.