The invention discloses a preparation method of polyphenyl ether thioether sulfoxide. The polyphenyl ether thioether sulfoxide comprises the following ingredients: 4,4'-dyhydroxy diphenyl sulfide and 4,4'-dihalogen diphenylsulfoxide as the reaction monomer of which the mole ratio is 1: 1.02, 1.1-2.5mole / mole of 4,4'-dyhydroxy diphenyl sulfide as the assistant, 0.1-0.5 mole / mole of 4,4'-dyhydroxy diphenyl sulfide as the catalyst, 1000-2000ml / mole of 4,4'-dyhydroxy diphenyl sulfide as the solvent, and 300-500ml / mole of 4,4'-dyhydroxy diphenyl sulfide as the azeotropy dehydrating agent. The process comprises the following steps of: (1) adding the ingredients into a reaction contain and stirring under the protection of nitrogen at the room temperature, rising the temperature, heating, and dehydrating, ending the dehydration when the temperature reaches 130-150 DEG C, subsequently rising the temperature to 170-220 DEG C and carrying out the polymerization reaction, when the reaction is ended, cooling naturally to the room temperature and stopping stirring; and (2) pouring the mixture liquid formed by the polymerization reaction into precipitating agent, precipitating and filtering so as to obtain a filter cake, washing the filter cake and drying in vacuum so as to obtain the polyphenyl ether thioether sulfoxide; and the structural formula is: (FORMULA).