The invention discloses a method for the selective reaction of highly efficient catalytic oxidation of alkanes. Taking alkane as raw material, in trifluoroacetic acid and / or trifluoroacetic anhydride system, using copper salt-metal salt as catalytic system, reacting in the presence of oxidant, and selective catalytic oxidation reaction occurs; wherein the metal salt is lithium salt, One or more of sodium, potassium, cesium, calcium or magnesium salts. The metal salt of the present invention, as a catalyst assistant, is used in combination with a copper salt to significantly improve the reaction activity of the catalyst in the catalytic oxidation of alkanes, while ensuring high product yield, significantly reducing the amount of the catalyst and improving its catalytic efficiency. Taking methane as an example, using the above method to prepare methane trifluoroacetic acid, the highest yield is about 72%, and the selectivity is about 92%. The reaction process conditions are relatively mild, and the reaction can be performed at 90 degrees, and the obtained methyl trifluoroacetate can be subjected to various transformations according to literature methods, such as hydrolysis into trifluoroacetic acid and methanol.