The invention provides a method for synthesizing (E)-(2-(phenylsulfonyl)vinyl)benzene and a derivative thereof. The method adopts styrene or a derivative of styrene as a reactant A and sodium benzenesulfinate or a derivative of sodium benzenesulfinate as a reactant B, and the reactant A and the reactant B react under the oxidation of persulphate to generate (E)-(2-(acyl)vinyl)benzene and the derivative thereof. Compared with the conventional method utilizing thioether oxidation, sulfur dioxide addition, Friedel-Crafts sulfonylation and transition metal catalysis coupling, the method increasesyield, and since the method utilizes relatively cheap persulphate as oxidant to carry out reaction, the cost of synthesis is reduced.