This invention relates to a process for preparing a catalyst useful for mercaptan synthesis, the catalyst prepared by said process, and the method of using said catalyst in the selective synthesis of mercaptans. More particularly, it relates to the process of preparing .alpha.-and/or .beta.-alumina trihydrates on an aluminum containing support or carrier and thereafter sulfiding the trihydrates, the product of said process, and the use of such product in the reaction of alcohols or ethers with hydrogen sulfide at elevated temperature to selectively produce the corresponding mercaptan.