The invention discloses a catalytic oxidation synthesis method of dicyclopentadiene dioxide. According to the method, dicyclopentadiene is used as a reaction raw material, hydrogen peroxide is used asan oxidant, poly o-halogenated styrene-divinylbenzene quaternary phosphonium salt type anion exchange resin supported heteropoly acid or peroxoheteropolyacid is used as a catalyst, and an epoxidationreaction is performed by using a fixed bed or a batch tank reactor to obtain dicyclopentadiene dioxide, wherein the reaction temperature of the epoxidation reaction is 30-80 DEG C, the reaction pressure is 0.1-6.0 MPa, the reaction time is 8-20 h, and a molar ratio of dicyclopentadiene to hydrogen peroxide is 1:2-1:4. According to the present invention, the method is simple, the catalyst has advantages of good heat resistance, stable service life and environmental friendliness, and the yield of the target product is more than 90%.