Thermal oxidation of Ti6Al4V was carried out at 700 °C for 5 h in air atmosphere. The characteristics of morphology and structure, micro-hardness, and tribocorrosion behavior in 0.9 wt.% NaCl solution of thermally oxidized Ti6Al4V alloys were investigated and compared with those of the untreated one. The scanning electron microscope (SEM) and glow discharge spectrometer (GDS) results reveal that the oxide layer is completely coated on the substrate, which is a bilayer structure consisted of oxide film and oxygen diffusion zone (ODZ). X-ray diffraction (XRD) and Raman measurements reveal the rutile phase as the dominant phase. The micro-hardness and surface roughness (R_a) increase about 1.63 and 4 times than those of the untreated one. Thermally oxidized sample obtains corrosion and tribocorrosion resistance property in 0.9 wt.% NaCl solution. The corrosion potential has a more than 500 mV anodic shift, the corrosion current density decreases about 80%. The total material loss volume is reduced by almost an order of magnitude under tribocorrosion behavior, which is due to the improvement of the micro-hardness of the oxide layer and ODZ that reduce the corrosion and the synergistic effect of corrosion and wear.