Polyimide composites filled with aramid fiber (AF) and polytetrafluoroethylene (PTFE) were prepared by hot press molding. The thermal, mechanical, and tribological properties of the composites were studied systematically. The friction and wear behavior, sliding against GCr15 steel balls, were evaluated in a ground-based wear in space simulation facility using a ball-on-disk tribosystem. The morphologies of the worn surfaces during the sliding process of the composites were analyzed by scanning electron microscopy to reveal the wear mechanism. It was found that the heat-resisting performance and the hardness of the composites were minimally affected by the additives. The flexural strength of polyimide/AF/PTFE (PI-3) decreased when PTFE was added. The wear resistance increased and the coefficient of friction decreased due to the effect of both fillers. In vacuum, the friction coefficients of polyimide (PI-1), polyimide/AF (PI-2), and PI-3 increased slightly with sliding velocity, while the opposite results were obtained in air. With the increase of air pressure the friction coefficients of the samples increased.