The shuttle and sluggish conversion kinetics of polysulfides (LiPS) significantly hinder the sulfur utilization and cycle performance of Li–S batteries. Herein, reduced Graphene Oxide supported Cobalt phthalocyanines(CoPc/rGO) and its skeleton Nitrogen substituent Cobalt Tetrapyridinoporphyrazine (CoTAP/rGO), are fabricated using a preform-solid synthesis process. When employed as separator modification, the CoTAP/rGO can capture and electrocatalyze LiPS by the active central Co–N4 units. And the Co–N4 sites are proved that can augment the LiPS redox kinetics especially the oxidation as well as the Li + diffusion rate. The introduced substituent N atoms in the skeleton match the LiPS redox ability and further enhance the Li + diffusion ability. Distribution of relaxation time (DRT) analysis shows that CoTAP nanoparticles can reduce the resistance of LiPS as well as Li + diffusion in Li2S precipitation procedure, accomplishing the loose three dimension deposition on cathode. As a result, the CoTAP/rGO separator exhibits a high initial capacity of 1132.7 mAh g−1 at 0.2C, excellent rate capacity of 672.5 mAh g−1 at 5C and superior long-term stability with a low capacity decay of 0.57 ‰ at 2C after 500 cycles.