Space exploitation and development need high-performance polymer based tribo-materials in order to reduce the weight and improve the reliability of mechanical moving components. However, the wear resistance of polymer composites will decrease after space irradiation. In order to improve the anti-irradiation and wear resistance, the high performance polyimide (PI) composites reinforced with aramid fibers (AF), filled with polytetrafluoroethylene (PTFE) and Al2O3were designed and prepared using hot press sintering. The effect of the individual atomic oxygen or proton irradiation as well as both on the tribological properties of the PI composites were systematically investigated against Si3N4 ball on a ball-on-disk test rig under simulating space environment system, and coefficient of friction and wear rate were considered as responses. The worn surfaces of the composites were observed by scanning electrical microscopy to reveal wear mechanisms of the materials’ damage. Experimental results indicated that the wear rate of the PTFE/AF/PI greatly increased after atomic oxygen and proton irradiation due to oxidation degradation effect on the polymer matrix. However, filling Al2O3 nano-particles into polyimide matrix can improve the wear resistance because of oxidation layer, gradually formulated during the process of atomic oxygen irradiation, which can protect the polymer composites and avoid further oxidation. This study will expect to provide the helpful guidance for designing high performance polymer based frictional materials in the application of space science.