The work aims to enhance the interfacial bonding strength of graphite (Gr) and phenolic resin (PF) matrix, and improve the tribological properties of PF composites. Copper-coated Gr was prepared by high-temperature infiltration and Gr-PF composites were also prepared. The effect of copper-coated Gr on tribological properties of PF composites was studied and the tribological properties of copper/Gr filled PF composites with the same component were compared. The friction and wear morphologies were analyzed by SEM, EDS and optical microscopy (OM) to study the wear mechanism. After the Gr surface was treated with copper, the state of copper altered from dispersed aggregation state into attached state and the prepared copper-coated Gr particles had high dispersion and good shape. Gr was closely bonded with PF matrix in copper-coated Gr-PF composites, thus maintaining the continuous phase structure of phenolic resin. The friction and wear surface was relatively flat and the average wear rate of copper-coated Gr-PF composites was 3.98×10?6 mm3/(N.m). The instantaneous friction coefficient fluctuated slightly and the main wear mechanism was adhesive wear. The copper/Gr filled PE composites prepared with the same component had poor interfacial bonding. The friction and wear surface had more cracks, the average wear rate of copper/Gr-PF composites was 7.80×10?6 mm3/(N.m), the instantaneous friction coefficient fluctuated greatly and the main wear mechanisms were adhesive wear and abrasive wear. The treatment of Gr surface by copper can not only enhance the interfacial bonding strength of graphite (Gr) and phenolic resin (PF), but also improve the corrosion resistance and friction stability of PF composites effectively.