In this article, thermosetting polyimide (TPI) composites based on two ideal ingredients (graphite/graphene-like carbon nitride, g-C3N4) were designed with different fibers and their tribological performance was comprehensively investigated at different high temperatures. It was found that the synergistic effect between solid lubricants graphite blended with g-C3N4 and reinforced fibers on friction and wear performance. Extremely lower friction and wear behavior of TPI composite is attained with aramid pulps (APs) at high temperatures. More importantly, an obvious transition of wear rate and friction took place with aramid pulps under 200 degrees C. When the cross-sections of the transfer films were analyzed using focused ion beam transmission electron microscopy (FIB-TEM) and X-ray photoelectron spectroscopy (XPS), it was found that graphite and g-C3N4 combined with APs led to simultaneous improvement in load-carrying capability of TPI matrix and durability of tribofilms subjected to complex physical and chemical reaction. Our work discloses a route for developing the TPI composite exposed to high temperatures with extremely lower friction and wear rate.