The invention relates to a synthesis method of a spiro-compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane. The synthetic route is 1,3-dibromo-2,2-di(bromomethyl)propane, 1,3-magnesium dibromide-2,2-di(magnesium bromide methyl)propane, 1,3-dicarboxyl-2,2-di(acetoxy)propane, and 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane. The 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane can be used as a novel expansion curing agent for an epoxy resin to reduce the volume shrinkage of the system to 0-1%, thereby overcoming the defect of poor mechanical properties of the epoxy resin cured by aliphatic acid anhydride, and improving the problem of volume shrinkage of the material. The invention is mainly used in the fields of epoxy resin casting and composite materials thereof.