In contrast with the well-developed radical thiol-ene reaction to access anti-Markovnikov-type products, the research on the catalytic Markovnikov-selective hydrothiolation of alkenes is very restricted. Because of the catalyst poisoning of metal catalysts by organosulfur compounds, limited examples of transition-metal-catalyzed thiol-ene reactions have been reported. However, in this work, a directing-group-assisted hydrothiolation of styrenes with thiols by photoredox/cobalt catalysis is found to proceed smoothly to afford Markovnikov-type sulfides with excellent regioselectivity.