The composite material HPW/NH2-Al2O3 was successfully prepared by immobilization of phosphotungstic acid H3PW12O40 (HPW) on the surface of amino functionalized spherical millimeter-sized mesoporous gamma-Al2O3 beads (NH2-Al2O3), that featured high specific surface area, remarkable enhanced mechanical strength, chemical stability and low cost. This composite material was characterized by Fourier Transform Infrared Spectroscopy (FTIR), X-ray diffraction (XRD), Brunner-Emmet-Teller (BET) and mechanical strength measurements. The experimental results showed that introduction of -NH2 group in between HPW and Al2O3 surface not only provide strong binding sites for catalytic centers HPW to get high dispersion on the carrier surface but also prevent HPW from structural decomposition. As a consequence, the prepared HPW/NH2-Al2O3 exhibited excellent catalytic performance in the oxidative desulfurization of model oil composed of dibenzothiophene (DBT) and n-octane. The 350 ppmws of sulfur content in 20 mL of n-octane can be dropped down to 2.8 ppmws in 2 h using 60 mg of HPW/NH2-Al2O3 catalyst under the optimal conditions. Remarkably, the catalyst can be conveniently recycled by simple decantation method. After 10 times recycling, the oxidation desulfurization efficiency just dropped down slightly from 99.2% to 98.6%. The results indicate that synthesized HPW/NH2-Al2O3 beads have great potential as a catalyst in oxidative desulfurization for special practical applications. (C) 2016 Elsevier Ltd. All rights reserved.