Methanol reaction with H2S on tungsten- and potassium-promoted alumina was studied in the absence of any diffusional restrictions. We have found that on both W/Al2O3 and KW/Al2O3 catalysts methanol reacts with H2S to produce methyl mercaptan, which may convert to dimethyl sulfide through either interaction with the second molecule of methanol or disproportionation. Methanol dehydration yields dimethyl ether. For KW/Al2O3 catalyst, the generation of methyl mercaptan dominates. Adsorption data permitted us to suggest a mechanism of methanol reaction with H2S. According to this mechanism reaction proceeds via the rapid methoxylation of catalyst surface and further interaction of CH3O groups with the activated H2S, CH3SH, and CH3OH. The kinetic equations obtained describe fairly well the reaction on the inhomogeneous catalyst surface.