Lithium perchlorate (LiClO4), used as an electrolyte salt for lithium–sulfur batteries, has been shown to give rise to the effective inhibition of the chemical polysulfide shuttle and thereby to enhance the coulombic efficiency through the stabilized charge process. In 1,2-dimethoxy ethane (DME)/1,3-dioxolane (DOL) (50:50 by volume), LiClO4 showed the lowest charge-transfer resistance among the various lithium salts studied and demonstrated the highest coulombic efficiency with an extreme reduction in the polysulfide shuttle. The origin of this behavior is considered to be the rapid formation of a passivation layer on the surface of the lithium metal anode. Hence, as well as being a good electrolyte salt in itself, LiClO4 is shown to be an effective polysulfide shuttle inhibitor.