A series of novel dispersed V2O5@Carbon composites, in which vanadium existed not only on the surface of carbon, but also in the matrix, were synthesized in situ from ammonium metavanadate (NH4VO3) and ethylenediaminetetraacetic acid disodium salt dihydrate (EDTA-2Na). The structures and properties of prepared catalysts were characterized by diverse techniques. An efficient process for catalytic oxidative desulfurization with V2O5@Carbon and cumene hydroperoxide (CHP) was investigated. V2O5@Carbons is superior to the physically supported catalysts in reusability and stability. Results show that 99.8 % sulfur in fuel can be removed and the catalyst can be recycled 7 times with no significant decrease in the desulfurization efficiency. A possible reaction mechanism is proposed, in which V(V)=O was oxidized to peroxo compounds (V(O)2) by CHP along with forming the 2-phenyl-2-propanol. The V(O)2 further cleaved to form electrophilic reactive VIV-O-O. species which could oxidize sulfur compounds to corresponding sulfones.