Li-S batteries are considered as one of the most promising battery systems because of their large theoretical capacity and high energy density. However, the "shuttle effect" of soluble polysulfides and sluggish electrochemical redox kinetics of Li-S batteries could cause a broken electrode structure and poor electrochemical performance. Herein, a high-performance and stable Li-S battery has been demonstrated by employing organo-polysulfide chain modified acetylene black (ABPS) as the coating layer on the separator. In addition to the traditional advantages of fast electron transport and polysulfide-interception ability of the carbon coating layer, the grafted organo-polysulfide chain endows the ABPS coating layer with permselectivity for lithium ion against polysulfides, electrocatalytic ability for the sluggish redox kinetics and self-repairing ability for the broken electrode. Hence, the battery prepared using an ABPS-coated separator delivers the best cycling performance (970 mA h g −1 at 0.2 C after 100 cycles) and rate performance (805 mA h g −1 at 2 C) as compared to the cells using acetylene black (AB)-coated or Celgard separators. Moreover, the Li-S battery prepared using an ABPS-coated separator exhibits a stable cycling performance at 1 C over 500 cycles with a low degradation of 0.04% per cycle, and a high coulombic efficiency (near 100%). Furthermore, as the sulfur loading was increased to 6.8 mg cm −2 , the Li-S battery using the ABPS-coated separator still could deliver a high areal capacity of 6.03 mA h cm −2 with a low electrolyte/sulfur ratio (E/S = 4, μL electrolyte mg S −1 ) after 170 cycles. Significantly, ABPS is an effective coating layer material for improving and stabilizing Li-S batteries. A novel carbon-coating layer material through grafting an organo-polysulfide chain on the carbon matrix (ABPS) was proposed for solving the sluggish electrochemical redox kinetics and repairing the broken electrode of high-loading Li-S batteries.