Entrapping polysulfide from dissolution into electrolyte by strong chemisorption of polar materials has been widely reported in lithium-sulfur (Li-S) battery. Here, for the first time, zinc sulfide (ZnS) was demonstrated as an activation catalyst in Li-S battery to suppress the soluble polysulfide shuttle effect by powering kinetics redox reactions of lithium polysulfide/sulfide. Kinetic analyses comprehensively identify that ZnS not only facilities polysulfide redox kinetics in liquid phase (Li2S8→Li2S6→Li2S4), but also promotes the effective decompositions of lithium sulfide (Li2S). Furthermore, first-principle calculations confirm that the low lithium ion diffusion barrier on the surface of ZnS promotes the redox reaction between lithium ion and sulfur species; and the low migration energy barrier of polysulfide on its surface guarantees the fast diffussion of polysulfides from the ZnS surface to the nearby conductive substrate, thus effectively smoothes polysulfides’ entrapping-diffusion-conversion mechanism across the ZnS interface, resulting in the highly reversible electrochemical performance. As evidenced by the ex situ SEM and visible experiment, the reaction between migrated sulfur species and lithium anode was significantly alleviated, and the insulating Li2S/Li2S2 was uniformly deposited on the ZnS-CB/S cathode. This ZnS cathode based Li-S battery exhibits outstanding performance including an excellent retained discharge specific capacity of 589 mA h gsul−1 with the high sulfur loading of 7 mg cm−2 (200 cycles) and extended cycling stability at the high current rate of 2 C, 5 C (632, 388 mA h gsul−1 after 1000 cycles).