Thiophene, due to its poison, together with its combustion products which causes air pollution and highly toxic characteristic itself, attracted more and more attention to remove from gasoline and some high concentration systems. As the purpose of achieving the novel method of de-thiophene assisted by SO 4 2− /ZrO 2 (SZ), three reactions about thiophene in different atmosphere at room temperature and atmospheric pressure were investigated. SO 4 2− /ZrO 2 catalyst were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), Fourier transformation infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscope (SEM). The products were detected by gas chromatography–mass spectrometry (GC–MS). XP spectra show that ozone-catalyst system (SZO) have two forms of sulfur element (S 6+ and S 2− ) on the catalyst surface, which distinguished from that of air-catalyst system (SZA) and blank-catalyst system (SZB) (S 6+ ). And the results of GC–MS exhibited that some new compounds has been produced under this extremely mild condition. Especially, many kinds of sulfur compounds containing oxygen, that is easier to be extracted by oxidative desulfurization (ODS), have been detected in the SZA-1.5h and SZB-3h system. In addition, some long chain hydrocarbons have also been detected. While in SZO-0.5h system, only long chain hydrocarbons were found. The results show that total efficiency of desulfurization from thiophene with ozone near to 100% can be obtained with the SO 4 2− /ZrO 2 catalytic oxidation reaction.