Abstract Lithium–sulfur (Li–S) batteries are considered as a promising next‐generation energy storage technology due to its high energy density over 2500 Wh kg −1 and low cost. Its development and application require to overcome several obstacles including the large volume change, the low electrical conductivity of S/Li 2 S, and the shuttle effect of lithium polysulfides (LIPSs). In this work, the hollow N‐doped carbon spheres (NHCS) decorated with nanosized SnS 2 (NHCS‐SnS 2 ) are synthesized and investigated to host sulfur used as the cathode for Li–S batteries. Highly conductive NHCS offer a large specific surface area and robust confinement for active material S, while SnS 2 nanoparticles provide efficient chemisorption of LIPSs and promote the deposition of solid Li 2 S. The NHCS‐SnS 2 /S cathode materials deliver a high discharge capacity 1344 mAh g −1 at 0.2 C and a low capacity decay over 200 cycles at 0.5 C. The outstanding cycling stability at 0.2 C with high sulfur loading of 3.0–3.1 mg cm −2 can also be readily attained. The excellent electrochemical performance is attributed to possible triple phase catalytic effect of NHCS‐SnS 2 and electrolyte, and such structure permits the full utilization of active materials from S 8 to Li 2 S.