A process for selectively making 2-thiols from alpha olefins is described. The process includes contacting a linear or branched alpha olefin having with H.sub.2S in the presence of a catalyst and recovering the 2-thiol from a product mixture. The catalyst includes a support and at least one metal selected from Group IIIA-VIIIA and the branched olefin is branched at the 3-position or higher with respect to the olefin double bond. Compositions wherein the 2-thiols are substantially free of 1-thiol and 3-thiol isomers are also described.