Abstract UiO‐66(Zr) as a member of metal‐organic frameworks (MOFs) has received much attention because of its advantages such as high surface area, good thermal, and chemical stability. However, pristine UiO‐66(Zr) as catalyst is inactive in some catalytic reactions due to the lack of active sites. In this work, we report that Ce‐doped UiO‐66(Zr) has been successfully synthesized under solvent‐free conditions. The obtained materials are characterized by various techniques. The results indicate that the incorporation of Ce species could greatly enhance the catalytic performance of UiO‐66(Zr) in the oxidative desulfurization of dibenzothiophene mainly owing to the creation of more active sites. Additionally, it is demonstrated that Ce‐doped UiO‐66(Zr) is a heterogeneous catalyst and can be reused.