Hierarchically porous silica (NKM-5) was used as support to load different amounts of Mo to prepare xMo/NKM5 catalysts (x was the weight percentage of Mo added during synthesis) by wetness impregnation method. Due to the hierarchically porous architecture and highly dispersed molybdenum oxide, 3Mo/NKM-5 with Mo loading of 3 wt% exhibited outstanding oxidative desulfurization activity. Complete conversion of 500 ppm dibenzothiophene was achieved within 20 min at room temperature, and the turnover frequency value was determined to be 28.0 h(-1) after 2 min of reaction. Furthermore, xMo/NKM-5 possessed a superior adsorptive performance for oxidative product dibenzothiophene sulfone, achieving adsorption rate of 77.7%-85.5% through oxidative adsorptive process. Hierarchically porous xMo/NKM-5 materials with the advantages of low cost, high activity, and excellent adsorptive capacity, are expected to be potential candidates for industrial desulfurization process.