The thiolation of dimethyl sulfide with H 2 S over a variety of tungsten–zirconia (WO 3 /ZrO 2 ) catalysts with different contents of WO 3 was studied. The maximum yield of methanethiol was obtained at the reaction temperature of 633K in the presence of 10wt.%WO 3 /ZrO 2 catalyst. XRD, BET and TPD characterization results reveal that supporting WO 3 species on ZrO 2 gives rise to the improvement of both in structure stability and surface acidity. The MT yield increased first and then decreased with the increase of reaction temperature for all of the catalysts due to the decomposition of methanethiol and dimethyl sulfide. The optimum loading of WO 3 was found to be 5–10wt.% (with a surface density of 3.5–4.5w-atomnm −2 ). Furthermore, the WO 3 /ZrO 2 catalyst exhibits high resistance to water.