In the present work, the Cr-AlSi12 composite coatings were successfully synthesized on the Ti-6Al-4V alloy substrate by using the mechanical alloying method. The effects of raw Cr particle size, milling duration, and annealing treatment on the preparation of the coatings were investigated. The asprepared coatings consisted of the inner coating layer with coarse Cr particles and the outer coating layer with refined and highly homogenized structure. The annealing treatment could promote element diffusion and alloying; it was favorable to the densification and oxidation resistance of the coatings. There is a highly densified alloyed layer in the outer coating. The annealed coating showed excellent friction and wear resistance. After the oxidation process, the annealed coating showed the best high-temperature oxidation resistance. The oxidized annealed coating exhibited four layers, which included the thin Al 2 O 3 oxide film, the homogenized alloyed layer, the composite layer consisted of Al 2 O 3 and coarse Cr particles surrounded by alloyed layer, and the Al 3 Ti diffusion layer. This was favorable to the improvement of high-temperature oxidation resistance. The oxidation process of the annealed coating was elaborated.