A series of V2O5/TiO2 catalysts with high vanadium loading (6.0 ∼ 43.9 wt%) were prepared by wet impregnation over metal–organic framework (MOF) MIL-125(Ti) support following calcination, and were tested for catalytic combustion of 100 ppm chlorobenzene. Taking advantage of MIL-125(Ti) with high surface area, copious catalytically active VOx species generated in the case of high vanadium loading, among which 0.4VTi, 0.6VTi and 0.8VTi showed 100% chlorobenzene conversion at 250 °C. The effect of vanadium loading on the catalysts have been characterized by means of XRD, SEM, TEM, ICP-OES, N2 adsorption–desorption at 77 K, Raman, NH3-TPD and H2-TPR. The reaction mechanism of chlorobenzene over the as-prepared catalysts was also proposed by in situ DRIFTS.