Tungsten-copper (W-Cu) composites are used as high temperature frictional materials under special service conditions for electromagnetic gun rail and precision guide for rolled pieces due to their good ablation resistance and electrical conductivity. However, they have poor wear resistance at elevated temperatures. In this paper, surface carburization method was applied on the W-20 wt%Cu composite to investigate the mechanisms of carburization and its effects on the high temperature friction behavior of composite. Carburization process has been done at a temperature of 1100 °C for 30 h. The obtained results showed that carburizing at 1100 °C with a dwelling time of 30 h resulted into formation of a carburized layer and a dense intermediate sub-layer on the substrate. Also, the surface carburized layer with a thickness of about 70 μm composed of mixed phases of graphite, WC and W2C. The hardness of carburized layer (~HV454) was significantly higher than that of substrate (HV223). Also, bending strength of the carburized W-Cu composites has been significantly improved, although their electrical conductivity and tensile strength was decreased slightly. The carburization mechanism of the W-Cu composites was found to be dominant by carbon atom diffusion through reaction with W atoms and formation of surface liquid copper, which promoted migration and diffusion of tungsten and carbon at high temperatures. Average coefficients of friction and wear rate of carburized W-Cu composites are all lower than these of un-carburized W-Cu composites owing to the presence of surface carburized layer. Also, formation of CuWO4 at high temperatures reduced the friction and wear resistance of the W-Cu composites.