A metal-free Cs2CO3-promoted hydrothiolation of alkynes with aryl thioureas for stereoselective synthesis of (Z)-vinyl sulfides has been reported. Vinyl thioethers were obtained without a metal catalyst in good yields via anti-Markovnikov and cis addition. The protocol features a broad substrate scope of the starting materials, high atom economy, good yields, and exclusive stereoselectivity, showing potential synthetic value for the synthesis of a diversity of (Z)-vinyl thioethers.