Polyimide composites have been extensively used as motion components under extreme conditions for their thermal stability and special self-lubricating performance. In the present study, Ag–Mo hybrids as lubricant fillers were incorporated into thermosetting polyimide to prepare a new type of tribo-materials (TPI-1) at high temperature. Comprehensive investigations at different temperatures reveal that the newly developed TPI-1 exhibits a better reduction in friction and wear rate below 100 ℃, but all of them increase significantly when the bulk temperature exceeds 250℃. The wear mechanisms demonstrated that sandwich-like tribofilms with different layers were established at different temperatures, which was further verified by characterization of scanning electron microscope (SEM), Raman spectroscopy, and transmission electron microscope (TEM). Considering the high-performance TPI coupled with Ag–Mo hybrids, we anticipate that further exploration would provide guidance for designing TPI tribo-materials that would be used at high temperatures.