A kind of highly active TiO2 was prepared and applied in the extractive and catalytic oxidative desulfurization (ECODS) system. The catalyst was synthesized through a simple method and characterized by X-ray powder diffraction (XRD), Raman, Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS). Various of reaction conditions were investigated on the removal of dibenzothiophene (DBT), and a sulfur removal of 99.1% was obtained under 40 degrees C in 90 min. In addition, electron spin resonance (ESR) spectroscopy and gas chromatography-mass spectrometer (GC-MS) measurements were employed to investigate the reaction mechanism. It was proved that superoxide radical (center dot O-2(-)) was the active oxygen species and DBTO2 was the only oxidation product of DBT in the ECODS system. The recycling experiments indicated that sulfur removal could still reach 95.5% after 12 times. (C) 2015 Elsevier Ltd. All rights reserved.