Thiophene is a typical thiophenenic sulfur compound that exists in coking benzene. In this paper, investigate oxidation chlorination of thiophene in coking benzene. Potassium permanganate was combined with hydrochloric acid for a new KMnO4/HCl system of oxidation desulfurization. The preliminary results show that the thiophene in the benzene cannot be deep oxidized desulfurization alone potassium permanganate solution even at acetum. The thiophene in the coking benzene could be mostly converted by using KMnO4/HCl system. In suitable reaction conditions thiophene’s removal rate can reach more than 93%.