The basic features of the reaction of thiol synthesis from hydrogen sulfide and methanol, n-propanol, n-butanol, or n-dodecanol in the presence of acid-base catalysts was studied. The catalysts with paired surface sites-weak Lewis acid sites and strong base sites-have a low activity but are selective in thiol formation. The catalysts with strong acid sites exhibited a high activity in the conversion of alcohols but were not selective in the formation of thiols. In the presence of proton-donor catalysts, the thiolation of methanol alone took place; other alcohols underwent only dehydration. The thiolation of methanol on various catalysts yielded dimethyl sulfide along with metanethiol; no dialkyl sulfides was produced in the reaction of hydrogen sulfide with higher alcohols.