The kinetics and stability of the redox of lithium polysulfides (LiPSs) fundamentally determine the overall performance of lithium–sulfur (Li–S) batteries. Inspired by theoretical predictions, we herein validated the existence of a strong electrostatic affinity between polymeric carbon nitride (p-C₃N₄) and LiPSs, that can not only stabilize the redox cycling of LiPSs, but also enhance their redox kinetics. As a result, utilization of p-C₃N₄ in a Li–S battery has brought much improved performance in the aspects of high capacity and low capacity fading over prolonged cycling. Especially upon the application of p-C₃N₄, the kinetic barrier of the LiPS redox reactions has been significantly reduced, which has thus resulted in a better rate performance. Further density functional theory simulations have revealed that the origin of such kinetic enhancement was from the distortion of molecular configurations of the LiPSs anchored on p-C₃N₄. Therefore, this proof-of-concept study opens up a promising avenue to improve the performance of Li–S batteries by accelerating their fundamental electrochemical redox processes, which also has the potential to be applied in other electrochemical energy storage/conversion systems.