Tribological behaviors of various polyimide (PI) composites when rubbing with medium carbon steel (MCS35) and NiCrBSi, were comprehensively investigated. When the conventional PI composite filled with carbon fibers and graphite was concerned, the carbon-based tribofilm formed on NiCrBSi surface resulted in obvious friction-and wear-reduction. However, no lubricating tribofilm was formed on MCS35 surface. Chelation of polymeric molecular radicals with the metallic counterparts was identified on the worn surfaces. Theoretical calculations corroborated that the Ni-based metal-organic compound showed a higher stability than the Fe-based one. With respect to the sliding of the hybrid nanocomposites containing silica or h-BN nanoparticles, the nanoparticles released onto the interface significantly mitigated tribo-oxidation of metallic counterparts, and were finally tribo-sintered into a compact layer after being mixed with remnant polymer and tribo-oxidation products. The effect of counterpart material was less pronounced for the tribological mechanisms of the nanocomposites than for the conventional composite.