Creation of defects in metal–organic frameworks (MOFs) has been demonstrated to be of significance formany potential applications. MOF-808(Zr), as an important member of MOFs, has attracted extensiveattention due to its advantages such as high stability, large surface area and pore size. Therefore, thedevelopment of defective MOF-808(Zr) is of great interest. In this contribution, we report that MOF-808(Zr) with abundant defects can be fabricated by the fracture of partial ZrAO bonds in its structureby the treatment of NH4HCO3 solution. During the treatment, the effect of NH4HCO3 concentration andtreatment time on the structural properties of MOF-808(Zr) was investigated. The catalytic performanceof obtained materials was evaluated by the oxidative desulfurization reaction of dibenzothiophene. Theresults revealed that MOF-808(Zr) obtained under the conditions of 0.08 M NH4HCO3 and treatment timeof 10 min exhibited superior catalytic activity (124.8 mmol/h/g) at 60 C due to the formation of richdefect sites in MOF-808(Zr).