Recently, the resource utilization of agricultural biomass wastes for the preparation of a wide range of high-value-added chemicals and functional materials, especially heterogeneous catalysts, has received extensive attention from researchers. In this work, mesoporous WO
3/ZrO
2-SiO
2 catalysts are prepared by a two-step incipient-wetness impregnation method using agricultural biomass waste rice husk (RH) as both the silicon source and mesoporous template. The effects of different WO
3 and ZrO
2 loadings on the oxidative desulfurization (ODS) performance of samples are investigated, and the suitable WO
3 and ZrO
2 loadings are 11 and 30%, respectively. The relevant characterization results indicate that, compared to 11%WO
3/SiO
2, the introduction of ZrO
2 leads to the formation of stronger W-O-Zr bonds, which makes the tungsten species stabilized in the state of W
6+. The strong preferential interaction between Zr and W facilitates the formation of stable and highly dispersed WO
x clusters on the mesoporous ZrO
2-SiO
2 carrier. Furthermore, it also prevents the formation of WO
3 crystallites, significantly reducing their content and thus inhibiting the loss of the WO
3 component during cycling experiments. Therefore, the 11%WO
3/30%ZrO
2-SiO
2 sample shows excellent catalytic activity and recycling performance (DBT conversion reaches 99.2% after 8 cycles, with a turnover frequency of 12.7 h
–1; 4,6-DMDBT conversion reaches 99.0% after 7 cycles, with a turnover frequency of 6.3 h
–1). The kinetics of the ODS reactions are further investigated. The mechanism of the ODS reaction is explored through experiments involving leaching, quenching, and the capture of the active intermediate. Finally, a possible reaction mechanism for the ODS process for the 11%WO
3/30%ZrO
2-SiO
2 sample is proposed.
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