The composite catalysts of ZSM-5@t-ZrO2 and ZSM-5/t-ZrO2 were prepared by hydrothermal coating method and physical blending method, respectively. Taking catalysts of t-ZrO2 and ZSM-5 as reference, catalytic performance, physical and chemical properties of the composite catalysts with different structures were studied. On this basis, the effects of reaction temperature and presulfurization operation on the adsorption and conversion characteristics of methanol and hydrogen sulfide on ZSM-5@t-ZrO2 composite catalyst were studied by means of diffuse reflectance Fourier transform infrared spectroscopy. The results show that hydrothermal coating process modified the physical and chemical properties of ZSM-5@t-ZrO2 composite catalyst, thus improves the catalytic performance and deactivation resistance of carbon and sulfur deposition of methanol thiolation reaction. Under the conditions of reaction pressure of 1.0 MPa, reaction temperature of 380 ℃, presulfurization for 1 h and N2 flow rate of 100 mL/min, the methanol conversion, methanethiol selectivity and methanethiol yield are 92.02%, 90.56% and 82.76%, respectively. The rate control step of the thiolation reaction is the adsorption and dissociation of hydrogen sulfide molecules on the base sites of of ZSM-5@t-ZrO2 catalyst into sulfhydryl groups and then attacking methoxy groups. The reaction temperature of 380 ℃ and presulfurization operation are helpful to build the matching formation rate of sulfhydryl groups and methoxy groups, which not only enhances the catalytic performance but also reduces the formation rate of carbon and sulfur deposition effectively.