Co-based alloys are promising alternatives to replace the currently used tool steels in aluminum die-casting molds for producing sophisticated products. Although the reaction is significantly less severe compared to that of tool steels, bare Co-29Cr-6Mo (CCM) alloy is still gradually corroded under molten Al, leading to the local failure of the alloy due to the formation of intermetallic compounds between the matrix and molten Al. This study indicated that prior oxidation treatment at 750 °C on CCM alloy is beneficial in enhancing the corrosion resistance of the alloy to molten Al. The is more pronounced in the alloy after a longer oxidation treatment. However, after oxidation for longer than 24 h, the protectiveness of the film cannot be enhanced anymore. In addition, even after the full failure of the oxide film, the thickness loss rate of a sample with prior oxidation treatment is much lower than that of a bare sample. This can be attributed to the fact that network-aligned oxide particles of the cone structure boundary inhibit both the outwards movements of alloying elements and the dissolution of the intermetallic layer.