The invention discloses a preparation process of perfluoro-2-methyl-3-
pentanone, belonging to the technical field of preparation methods of perfluoroketone compounds in the field of organofluorine 
chemistry. The perfluoro-2-methyl-3-
pentanone is obtained by performing an epoxidation reaction and a catalytic 
isomerization reaction on perfluoro-2-methyl-
pentene serving as a 
raw material in sequence. The preparation process comprises the following steps: I, in a continuous 
liquid phase epoxidation reaction, mixing a corresponding proportion of aprotic polar 
solvent into a 
sodium hypochlorite solution to promote the reaction, increase the 
raw material conversion ratio and increase the 
reaction rate at least by 2-3 percent, wherein the step is characterized by easiness and convenience in operation, low 
equipment requirement and high reaction equipment efficiency; II, performing a continuous 
gas phase catalytic reaction, wherein the application of a 
solvent is effectively avoided, the cost and environmental 
pollution are lowered, the problems of the need of separating the 
solvent from a product in post-treatment, difficulty in recycling and treating the solvent and a catalyst, and the like are solved, and the product can be refined and purified more easily. The preparation process has the advantages of high process 
automation degree, easiness and convenience in operation, high product purity and high reaction equipment efficiency, and is suitable for industrial application.