Ultra-high-molecular-weight polyethylene (UHMWPE) reinforced with carbon fibre (CF) and filled with polyphenyl ester (POB) and nanosized copper (Cu) fillers was prepared by compression moulding. The tribological behaviours and the synergism of the incorporation of fibre and particulates were studied. The proportions of the reinforcement material ranged from 5 wt% to 25 wt%, the filler material of POB varied from 5 wt% to 25 wt% and the nanosized filler was from 4 wt% to 12 wt%. In the sample with CF only, the lowest wear rate was observed for the UHMWPE + 15% CF composite. The particulate filler further reduced the composite wear rate, and the lowest wear rate was found for the hybrid with CF, POB and nanosize Cu particles, that is, for the UHMWPE + 15% CF + 15% POB + 12% Cu composite. The particulate filler was added, and the coefficient of friction slightly increased. The transfer film formed on the metal counterface was studied using optical microscopy, and the topography of the transfer film was investigated using atomic force microscopy. Results showed that the transfer films were thin, compact and uniform on the metal counterfaces of the UHMWPE + 15% CF + 15% POB + 12% Cu composite. Worn surface morphologies of composites were studied using scanning electron microscopy. Results showed that the worn surface of the UHMWPE + 15% CF + 15% POB + 12% Cu composite was smoother and had better wear resistance than that of other composites.