Sluggish multiphase reaction kinetics and severe shuttle effect of lithium polysulfides (LiPSs) are two major challenges facing lithium-sulfur (Li-S) batteries, which largely prevent them from becoming a reality. Herein, a shell with catalytic function for sulfur cathode is in situ constructed through an ingenious electrochemical oxidative polymerization strategy by introducing hexafluorocyclotriphosphazene (HFPN) as additives, which suppresses the shuttle effect and promotes efficient sulfur conversion. The shell with abundant heteroatoms effectively confines polysulfides to the cathode matrix by chemically interacting with them to eliminate capacity degradation. Moreover, the shell exhibits high catalytic activities, which turns Li2S(2) into an activated state and facilitates its dissociation. The functionalized shell substantially advances the performance of Li-S batteries, thanks to efficient lithium-ion transportation and abundant adsorption-catalytic sites. As a result, Li-S batteries demonstrate superb resistance to self-discharge, ultrastable cycle performance, and greatly enhanced rate capability. Impressively, the batteries show an ultralow capacity decay rate of 0.034% throughout 700 cycles at 2C. They deliver a capacity of 517 mAh g-1 even at a 4C rate, exhibiting relieved electrochemical polarization and excellent sulfur utilization. This work provides an ingenious strategy to construct adsorption-catalytic nets for next-generation Li-S batteries with enhanced lifespan and electrochemical performance.