The effect of fullerene carbon (C60) on the tribological performance of polyimide (PI) composites was explored at different temperature conditions. The results demonstrate the addition of 1.0 wt% C60 can greatly enhance the tribological performance of PI/1.0C60. The friction coefficients and wear rates of 0.03/0.07 and 1.0 x 10(-5)/1.6 x 10(-5) mm(3)/Nm can be achieved at 100 ?/200 ?, respectively, reducing by 86.4%/50.0% and 28.6%/30.1% compared with pure PI. It demonstrated the polymer states influenced the lubricated and loading carry capability of the sliding interfaces at different temperatures. XPS results indicated tribo-oxidation and organic-inorganic chelation reaction dominated the tribofilm growth. Moreover, molecular dynamics simulation showed the C60 enables the shear of PI easily due to the decreased intermolecular forces.