Herein, the tribological performance, thermal and compression resistance behavior of polyimide (PI) reinforced by Fe(2)O(3)decorated reduced graphene is systematically investigated. The remarkable synergistic effect of Fe(2)O(3)decorated reduced graphene oxide (RGO) is demonstrated in its PI wear resistance, and PI/RGO/Fe(2)O(3)composites show good thermal stability and much higher compression resistant ability than PI, PI/RGO, and PI/Fe(2)O(3)composites when the filling contents are same. Additionally, the PI/RGO/Fe(2)O(3)composites also exhibited ultra-wear-resistant properties under high load condition, and the lowest wear rate is 3.18 x 10(-8)mm(3)N(-1)m(-1), which is an order of magnitude lower than that of pure PI. The investigation of its tribological mechanism also showed strong synergistic effect and interface force of Fe(2)O(3)decorated RGO, which contribute to its high-performance friction-reducing behaviors. These findings give an inside view to Fe(2)O(3)decorated RGO and its polyimide composites, and open an avenue for the graphene oxide (GO) based composite to act as compression wear-resisting solid fillers and lubricants when polymer composite with excellent compressive, thermal and tribological properties is required.