A novel copper-catalyzed hydrothioetherification of oxa(aza)bicyclic alkenes with potassium thioacetate and aryl or alkyl iodides to synthesize unsymmetrical thioethers has been developed. Notably, the reaction with complete diastereoselectivity went through a syn-selective addition process to give exo-adducts. In addition, this protocol exhibited high efficiency and good functional group tolerance to afford the target thioethers in moderate to good yields. Based on the results of mechanistic investigations, a plausible mechanism was proposed.