Herein, by introducing a VO group into the microstructure of phosphomolybdenic acid (PMA) and loading it onto MOF-808, a series of composite catalysts were obtained by reducing the V element with Vitamin C (ascorbic acid). V atoms exist in the secondary structural units of phosphomolybdic acid as [VO(HO)]H[PMoO]. Surprisingly, the VC-VO-PMA/MOF-808 completely removed DBT and 4,6-DMDBT from the simulated oil in 12 min. The EPR and XPS results verify the electronic structure and valence state of V in the composites. The oxygen vacancy and V generated by VC modification in VC-VO-PMA/MOF-808 have positive effects on the oxidation desulfurization (ODS) activity. Based on the design of the microstructure and electronic structure, this study provides a new paradigm for the development of readily available and efficient ODS catalysts.