The invention discloses a catalytic preparation method of dicyclopentadiene dioxide by quaternary ammonium heteropoly phosphato tungstate, which is characterized by comprising the following steps: epoxidation reaction: adding the raw materials of dicyclopentadiene, solvent I and quaternary ammonium heteropoly phosphato tungstate in a reactor, heating the temperature to 30-80 DEG C, stirring and dropwise adding aqueous hydrogen peroxide solution, and reacting for 3-36h under the temperature of 30-80 DEG C after dropwise adding; post-treatment: cooling the reacted materials to room temperature, evaporating solvent I by reduced pressure distillation and separating and removing water to obtain the mixture of the product and the quaternary ammonium heteropoly phosphato tungstate catalyst, dissolving and filtering the mixture by ethyl acetate to obtain filter cake, namely the recovered quaternary ammonium heteropoly phosphato tungstate catalyst, recovering ethyl acetate by performing reduced pressure distillation on filtrate to obtain the crude product, performing recrystallization on the crude product by solvent II, and drying to obtain the product. The invention has the advantages of convenient operation, high safety, small pollution, simple post treatment, and high product yield and purity.