The VSX/TiO2 composite layer was successfully prepared by adding Na2S and Na3VO4 into electrolytes through micro-arc oxidation (MAO) method. The structure, morphology and tribological properties were analyzed by X-ray diffraction, scanning electron microscopy and 3D true color microscopy. The results show that when the concentration of Na2S is 10-20 g/L, the thickness of VSx/TiO2 composite layer is the thickest, and the friction coefficient and volume wear are the lowest. The VSx/TiO2 composite layer in-situ prepared by MAO can improve the tribological properties of TC4 alloy at high temperature.