Diffusion reaction was a crucial route to enhance the wear resistance of Ti-6Al-4V alloys surface. In this work, the Ni/Cu/Ni composite layers were fabricated on the surface of Ti-6Al-4V alloy by electroplate craft, and then different annealing temperatures were applied to further optimize its tribological properties. The diffusion behaviors at various temperatures were systematically analyzed to reveal the physical mechanism of the enhanced tribological properties of the coatings. It was demonstrated that CuxTiy and NixTiy intermetallic compounds with high hardness and strength were produced in the Ni/Cu/Ni coating, which acted as the reinforcing phases and improved the microhardness, reduced the friction coefficient, and lessened the wear rate. Specially, this effect reached the maximum when the annealing temperature was 800 °C, showing excellent wear resistance. This work revealed the relationship between annealing temperatures and tribological properties of the Ni/Cu/Ni coating, and proposed wear mechanism, aiming to improve the surface performance of Ti-6Al-4V alloy by appropriate diffusion behavior.