The invention discloses a preparation method of 5-methyl-5-ethyl hexenoate. The method comprises the following steps: 1) adding ethyl acrylate, benzene and a catalyst into a four-neck flask, controlling the temperature to be 25-30 DEG C, introducing isobutene, preserving heat for 24-60 hours, adding a sodium bicarbonate aqueous solution, stirring for 0.5-1 hour, adding a mixed solution of hydrochloric acid and water, stirring for 0.5 hour, standing for 0.5 hour, layering, and washing with water to obtain a water layer and a benzene layer; and 2) adding the benzene layer into a barrel, adding adehydrating agent, dehydrating, concentrating, carrying out normal pressure distillation and reduced pressure distillation in sequence, and collecting the azeotropic fraction to obtain the 5-methyl-5-ethyl hexenoate. According to the preparation method of the 5-methyl-5-ethyl hexenoate, aluminum trichloride and tungsten hexachloride are synergistically used as catalysts, the total yield can reach46.7% or above, anhydrous sodium sulfate and n-butyl alcohol are used as dehydrating agents, and the product purity can reach 97.5% or above; and the preparation method disclosed by the invention issimple to operate and relatively low in cost.