A series of supported Mo-based catalysts for methanethiol synthesis from high H2S-containing syngas were investigated by kinetics and XPS, ESR characterization. The activity evaluating results show that upon the potassium-promoted Mo-based catalysts, the methanethiol will become dominant product of the reaction, and the activity sequence of several Mo-based catalysts for the reaction is as follows: K2MoO4/CoO/SiO2 > K2MoO4/SiO2 > MoO3/K2CO3/SiO2 > K2MoS4/SiO2 > MoS2/K2CO3/SiO2. In the ESR characterization of the catalysts used the resonant signals of "oxo-Mo(V)" and "thio-Mo(V)" can be detected. The XPS characterization indicates that mixed valence Mo species Mo4+, Mo5+ and Mo6+ and three kinds of S species S2-, (S-S)(2-) and S6+ exist in the catalysts. As a promoter CoO was introduced into Mo-based catalysts. It was observed that the addition of CoO leads to decrease of the amount of "oxo-Mo(V) " in the catalysts, but increase of the amount of "thio-Mo(V)", which may be connected with "Mo-S-K" phase or "Co-Mo-S-K" phase, meanwhile CoO in die catalyst was found to enhance the formation of S2-, but inhibit the formation of (S-S)(2-). It was found also that the methanethiol synthesis is favored if the peak intensity ratios of (Mo4+ + Mo5+)/Mo6+ and S2-/(S-S)(2-) are kept at about 0.75 and 1 level respectively. A possible mechanism about the relationship of CH3SH formation with "Mo-S-K" phase was proposed
