The invention discloses a method of synthesizing beta-iodovinylsulfone compound under iodine participation. Iodine and tert-butyl hydroperoxide are used as a co-catalyst, bis-substituted acetylene andaryl sulfonyl hydrazide are used as reaction materials, toluene is used as a solvent, stirring is performed at 50 DEG C for 12 h, and after the reaction is over, beta-iodovinylsulfone is acquired byprocessing. The method herein has no need for adding metal catalysts and has the advantages of low toxicity, good convenience of material manufacturing, good applicability of functional groups and thelike.