The development of new efficient strategies for the construction of the C-S bond has attracted considerable interest due to its presence in various crucial biological systems and pharmaceutical compounds. Alkene hydrothiolation is one of the simplest and most atom-economic methods for organosulfur synthesis. This review focuses on transition-metal-catalyzed C-S bond formation via alkene hydrothiolation with thiols and is divided into three sections covering 3d, 4d, and 5d transition-metal-catalyzed hydrothiolation re-ported from 2013 to the present. Synthetic methods, substrate scope, and reaction mechanisms are discussed. We aim to provide a concise overview of recent advances in the hydrothiolation of alkenes and hopefully encourage further exploration to fill the gaps. The current landscape suggests considerable potential for future innovation and discovery in this field.