The invention provides a preparation method of perfluorethyl isopropyl ketone. The preparation method specifically comprises the step of: with a hexafluoropropylene dipolymer mixture and perfluo-4-methyl-2-amylene or perfluo-2-methyl-2-amylene as raw materials, carrying out reaction processes such as olefin epoxidation, structural rearrangement of epoxide to prepare the perfluorethyl isopropyl ketone. An aprotic polar solvent, a catalyst and a phase transfer catalyst are used in a preparation process, high selectivity and high transformation rate of all steps of reactions are realized, and after a reaction mixture is simply separated so that an intermediate and a perfluorethyl isopropyl ketone product with high quality can be obtained. Meanwhile, a one-pot technology of double bond isomerization and epoxidation reaction is established. The preparation method provided by the invention has the characteristics that raw materials are easily available, the cost is low, reaction conditions are mild, operation is safe and simple, reaction selectivity and transformation rate are high, little environment influence is low; therefore, the preparation method is suitable for industrial application.