Nanostructured surface layer was produced on Ti-6Al-4V alloy by surface mechanical attrition treatment (SMAT) technique, and the composite ceramic coatings of surface nanocrystallization/ micro-arc oxidation (SNC/MAO) were prepared on the nanocrystallized surface of Ti-6Al-4V alloy by pulsed single-polar micro-arc oxidation in NaAlO2 solution. XRD, SEM and TEM techniques were used to investigate the phase and surface morphology of ceramic coatings and the influences on the surface state of the alloys. Meantime, the mechanical properties of Ti alloys were measured by tensile test. The results show that after the SMAT treatment for a short period of time, the surface layer was refined into ultrafine grains. The influences of the SMAT technique on the surface morphology of the ceramic coatings were also studied. The ceramic coatings are mainly composed of Al2TiO5, more compact and less porous than those untreated. The mechanical properties of Ti-6Al-4V alloy by SMAT technique are improved, compared with those untreated by SMAT technique.