The application of Li‐S batteries is hindered by low sulfur utilization and rapid capacity decay originating from slow electrochemical kinetics of polysulfide transformation to Li₂S at the second discharge plateau around 2.1 V and harsh shuttling effects for high‐S‐loading cathodes. Herein, a cobalt‐doped SnS₂ anchored on N‐doped carbon nanotube (NCNT@Co‐SnS₂) substrate is rationally designed as both a polysulfide shield to mitigate the shuttling effects and an electrocatalyst to improve the interconversion kinetics from polysulfides to Li₂S. As a result, high‐S‐loading cathodes are demonstrated to achieve good cycling stability with high sulfur utilization. It is shown that Co‐doping plays an important role in realizing high initial capacity and good capacity retention for Li‐S batteries. The S/NCNT@Co‐SnS₂ cell (3 mg cm⁻² sulfur loading) delivers a high initial specific capacity of 1337.1 mA h g⁻¹ (excluding the Co‐SnS₂ capacity contribution) and 1004.3 mA h g⁻¹ after 100 cycles at a current density of 1.3 mA cm⁻², while the counterpart cell (S/NCNT@SnS₂) only shows an initial capacity of 1074.7 and 843 mA h g⁻¹ at the 100th cycle. The synergy effect of polysulfide confinement and catalyzed polysulfide conversion provides an effective strategy in improving the electrochemical performance for high‐sulfur‐loading Li‐S batteries.