Abstract: The preparation method of a new type sulfur doped polystyrene was studied. Under the initiator of AIBN, homopolymer and copolymer with styrene were synthesized from p-chloromethyl styrene. The chloromethyl polystyrene can react with potassium ethyl xanthate to produce sulfur doped polystyrene. This method is simple and the condition of reaction is mild. The structures of the polymer were characterized by means of IR and 1H NMR. The relative molecular mass of polymer was detected by gel permeation chromatogram (GPC) and the doped amount of sulfur atom was analyzed by element analysis. At the same time, the performance of film formation was also studied. The initial results show that the polymers have a good film characteristic.The preparation method of a new type sulfur doped polystyrene was studied. Under the initiator of AIBN, homopolymer and copolymer with styrene were synthesized from p-chloromethyl styrene. The chloromethyl polystyrene can react with potassium ethyl xanthate to produce sulfur doped polystyrene. This method is simple and the condition of reaction is mild. The structures of the polymer were characterized by means of IR and 1H NMR. The relative molecular mass of polymer was detected by gel permeation chromatogram (GPC) and the doped amount of sulfur atom was analyzed by element analysis. At the same time, the performance of film formation was also studied. The initial results show that the polymers have a good film characteristic.