Among several re-visited chemistries, rechargeable lithium-sulfur (Li-S) batteries have gained attraction due to their high theoretical capacity, wider range of temperature operability, and low cost. However, Li/S batteries have several drawbacks such as low cycle life, poor coulombic efficiency, eventual poisoning of Li-anode, and high self-discharg. Though several strategies based porous carbon, metal oxide materials have been used as host structures for sulfur and its intermediate polysulfides, the week adsorption, low surface area & conductivity and its poor reaction kinetics hinders them to achieve stable Li-S performance. Here, we preset a novel “Se-S” interaction chemistry at the cathode surface to stabilize polysulfide shuttle process along with enhancement in its redox kinetics. The “Se-S” interaction between polysulfide intermediates and monolayer of selenides has been evaluated from the insitu spectro-electrochemical studies. The introduction of selenium based cathodes in the Li-S system is expected to open a new avenue for improving electrochemical performance.