In this paper, the nano-diamond decorated reduced graphene oxide (Diamond-RGO) and its polyimide (PI) composite, by using in situ polymerization method, are synthesized, respectively. The tribological study of Diamond-RGO/PI composite exhibits super anti-wear properties under dry sliding and high load condition: the lowest wear rate of 4.9 × 10-8mm3N-1m-1, which is extraordinarily lower than that of pure PI and RGO/PI composite, is obtained under load 100N. The tribological mechanism investigation shows that Diamond-RGO composite has a strong synergistic effect in the tribological process which contributes to form a uniform transfer film on the counterpart ring and thus significantly decrease the composite’s wear rate. Through molecular simulation, the shear behavior of the composite material indicates that the presence of the Diamond-RGO composite will obviously weaken the influence of the iron wall on the PI bulk phase molecular chain in the shear process. This confirms that the synergistic effect between nano-Diamond and RGO will improve its PI composite’s tribological performance on atomic level.