This paper described the synthesis of meso/macroporous phosphotungstic acid (HPW) /TiO2 catalyst with quatemary ammonium bromide and monodispersed polystyrene spheres (PS) as dual-template. The synthetic parameters, such as concentration of the templates and the alky chain length of quaternary ammonium bromide was studied carefully and optimized to generate catalyst with regulated porous features. The chemical properties of the catalyst was also investigated, X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) measurements confirmed the Keggin-type HPW were highly dispersed on the TiO2 framework. The optimal meso/macroporous HPW/TiO2 catalyst exhibited excellent catalytic activity in the oxidation of refractory sulphur compounds such as benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT). DBT was removed within 2 h at 30 degrees C under selected reaction conditions and the apparent activation energy for DBT oxidation was calculated to be 45.7 kJ/mol. The high ODS reaction rate of catalyst could be attributed to the combination of unique meso/macroporous architecture allowing for efficient mass transport of reactants and products in pore channel and its high surface area, large mesoporous size, and pore volume enabling sufficient exposure of catalytic active sites. Moreover, the meso/macroporous HPW/TiO2 catalyst also exhibited excellent reusability with no obviously degradation even after eight cycles.