In the present work, a commercial mesoporous gamma-Al2O3 with large specific surface area, high mechanical strength and good thermal stability was employed as the support for preparing a series of V2O5/gamma-Al2O3 materials with different loading amounts of V2O5. Ce and Pt were introduced in order to further promote the oxidative performances for catalytic combustion of benzene, a typical pollutant of various volatile organic compounds (VOCs) in industrial waste gases. To investigate the structure catalytic property relationship, these catalytic materials were systematically characterized by the XRD, N-2 adsorption/desorption, HRTEM, EDX, H-2-TPR and in-situ TPSR techniques. The results showed that the introduction of 10%wt Ce and 0.3%wt Pt significantly improved the catalytic oxidative activity and CO2 selectivity of the V2O5/gamma-Al2O3 catalysts for benzene combustion, due to the obvious enhanced redox property resulted from the metal metal and metal-support interaction as well as the high dispersion of the active components on gamma-Al2O3. Furthermore, the 0.3%Pt/10%Ce10%V/gamma-Al2O3 catalyst also represented good durability and resistance to water and Cl-poisoning during the long-time continuous reaction, implying that it deserved more attention and had good potential for industrial application.