A high‐surface‐area boehmite was used as the support for a series of vanadium phosphate catalysts. The catalysts were prepared by heating of V₂O₅ in an isobutyl alcohol and benzyl alcohol mixture at 140°C for 5 h to reduce V⁵⁺ to more active V⁴⁺ in the presence of phosphoric acid. Then a series of catalysts with various VPO loadings on boehmite were synthesized. The catalysts were characterized using various techniques. The catalysts were utilized for extraction combined with catalytic oxidation of dibenzothiophene. The important factors influencing the desulfurization process, including reaction time, temperature, H₂O₂, catalyst loading, catalyst amount and solvents, were systematically investigated. Under the optimized reaction conditions, i.e. 30 mg of catalyst loading at 50°C and in 60 min, sulfur removal reached 94%. The catalyst was recycled and reused five times.