The synthesis of poly(thio-1,4-phenylene) (PPS) at room temperature by the reaction of diphenyl disulfide with potassium persulfate (K2S2O8) in non-basic solvents, in the presence of trifluoromethanesulfonic acid, is reported. The reaction in chlorinated solvents, such as dichloromethane and tetrachloroethane, resulted in partial oxidation of sulfide to sulfoxide and sulfone. On the other hand, the polymerization proceeded well in nitrobenzene and the PPS formed was free of branches, crosslinks and thianthrene units. The molecular weight of the polymers formed in different solvents were in the range 2000-8000. The reaction proceeded under identical conditions with bis(2,6-dimethylphenyl) disulfide as well, but the polymer yield was lower.