Stabilizing polysulfide-shuttle process while ensuring high sulfur loading holds the key to realize high theoretical energy density (2500 Wh/kg) of lithium-sulfur (Li-S) batteries. Though several carbon based porous materials have been used as host structures for sulfur and its intermediate polysulfides, the week adsorption of polysulfides on carbon surface and its poor reaction kinetics limits them from practical application. Here, we preset a novel ‘electcatalysis’ approach to stabilize polysulfide shuttle process and also enhance its red-ox kinetics. Nature of electrocatalyst, pore-size distribution, concentration of polysulfides, temperature of the cell etc., on electrochemical properties will be discussed. We reveal substantial improvement in electrochemical properties such as specific capacity, rate capability, coulombic efficiency etc. and corroborate our findings with systematic experimental studies. Interaction between electrocatalyst and polysulfides has been evaluated by conducting X-ray photoelectron spectroscopy and electron microscopy studies at various electrochemical conditions. Thus, introducing a catalyst in the Li−S system will open a new avenue for improving electrochemical performance.