Catalyst-free Markovnikov-selective hydrothiolation of unactivated alkenes still remains a great challenge. Herein, we develop a catalyst/metal/solvent-free methodology for the Markovnikovhydrothiolation of unactivated alkenes with in situ prepared dithiocarbamic acids, providing a wide array of alkyl dithiocarbamates. A variety of terminal, internal, cyclic, and acyclic unactivated alkenes were applied