The invention provides a preparation method of 3, 4, 5-trimethylhydroquinone dialkanoate. The preparation method comprises the following steps: reacting in the presence of a catalyst and a cocatalystand carrying out esterification and rearrangement reaction on 2, 6, 6-trimethylcyclohexyl-2-ene-1, 4-diketone and an acylating agent to obtain the product, wherein the catalyst is selected from sulfuric acid, hydrochloric acid, phosphoric acid, fluoroboric acid, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, chloroacetic acid, BF3, BF3.OEt2, AlCl3, FeCl3, ZnCl2, TiCl4, SnCl2 and the like, and the cocatalyst is selected from nicotinic acid, 3-pyridylaldehyde, phenyl nicotinate, furoate nicotinate, 5-hydroxy-6-methyl nicotinic acid and 5-hydroxy-6-methyl ethyl nicotinate. The process has the advantages of easiness in industrialization, good selectivity, high product yield and the like.