The effect of vacuum heat treatment on the interface microstructure and tribological property of Cu‐coated Ti – 6Al – 4V alloy is investigated herein. After the vacuum heat treatment process, a diffusion layer is formed at the interface between the Cu coating and the Ti – 6Al – 4V substrate. The formed intermetallic compounds at the interface between the Ti – 6Al – 4V substrate and Cu coating are CuTi 2 , CuTi, Cu 4 Ti 3 , and β‐Cu 4 Ti. The activation energy of intermetallic compound growth in the diffusion zone of Cu‐coated Ti – 6Al – 4V is 126.0 kJ mol −1 , and the pre‐exponential factor is 0.1 m 2 s −1 . The tribological properties of the Cu‐coated Ti – 6Al – 4V alloy are best when subjected to diffusion treatment at 700 °C for 300 min, with weight loss reduced by 58.2% compared to the Ti – 6Al – 4V alloy. The wear resistance of the Ti – 6Al – 4V alloy can be enhanced by Cu coating and vacuum diffusion heat treatment, and the formation of the Cu – Ti intermetallic compound contributes to this improvement. These findings offer new insights for further advancements in the tribological properties of titanium alloys.