The work aims to improve the tribological properties of Ti6Al4V alloy. Oxidation ceramic coatings were prepared on the surface of Ti6Al4V substrate by micro-arc oxidation treatment in silicate-phosphate electrolyte with different concentrations of tungsten nano-powder. Micro-morphology of surface and cross section element distribution, phase constituents of the micro-arc oxidation coatings with different concentrations of tungsten nano-powder were analyzed by FE-SEM, EDS and XRD. Tribological properties were evaluated by rotational wear test. The addition of tungsten nano-powder in electrolyte could promote the growth of the coating, especially the approximate linear growth within the range of 0.5~2 g/L tungsten nano-powder in electrolyte, but the adhesion of tungsten nano-powder on the surface of the coating could increase roughness. Except rutile, anatase and Al2TiO5 in the micro-arc oxidation coatings, the content of tungsten nano-powder also increased as the particles in the electrolyte grew. The friction co-efficiency and specific wear rate of the composite coating prepared in the electrolyte with 6 g/L tungsten nano-powder reduced by 13.33% and 3.53% respectively. Tungsten nano-powder exists on composite coating surface by mechanical entrapment. Parts of particles enter the membrane with molten oxide and show signs of melting. The quality of the micro-arc oxidation coating surface prepared in electrolyte with 6 g/L tungsten nano-powder is improved, e. g. reduction of the micro-pores and cracks, and better wear resistance. Friction co-efficiency and specific wear rate are both lower than that of coating without tungsten nano-powder.