<p>The introduction of oxygen vacancies on the surface of catalysts is an important way to improve the performance of catalysis for oxidative desulfurization. In this study, Ni-doped CoMoO₄ catalysts with a significant number of oxygen vacancies were synthesized using hydrothermal methods. The structure of the catalysts was characterized through scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N₂ adsorption–desorption techniques, and UV–visible diffuse reflectance (UV–Vis DRS). Compared to CoMoO₄, the specific surface area of Ni-CoMoO₄ decreased, but the performance of catalysis is improved due to the increased number of oxygen vacancies. The oxidative desulfurization experiments showed that catalytic activity was significantly enhanced by Ni doping. The optimum reaction conditions were determined to be a Ni/Co molar ratio of 1:20, a reaction temperature of 110&#xa0;°C, a catalyst dose of 0.05 g, and an oxygen flow rate of 150 mL/min. The desulfurization rate of dibenzothiophene (DBT) in model oil could be as high as 96% under the optimum reaction conditions. The desulfurization mechanism of the catalyst was investigated by free radical-trapped experiments. This study proposes a novel strategy for oxidative desulfurization using metal-doped compounds with abundant oxygen vacancies as catalysts.</p> Graphical abstract <p>An inorganic material Ni-CoMoO₄ with a number of oxygen vacancies was synthesized by hydrothermal method and applied for removal of sulfur-containing compounds. It is necessary for ecological and environmental demands. This work provides a new idea for oxidative desulfurization using metal-doping compound containing a number of oxygen vacancies as catalysts.</p> <p></p>