Lithium–sulfur (Li–S) batteries are investigated intensively as a promising large‐scale energy storage system owing to their high theoretical energy density. However, the application of Li–S batteries is prevented by a series of primary problems, including low electronic conductivity, volumetric fluctuation, poor loading of sulfur, and shuttle effect caused by soluble lithium polysulfides. Here, a novel composite structure of sulfur nanoparticles attached to porous‐carbon nanotube (p‐CNT) encapsulated by hollow MnO2 nanoflakes film to form p‐CNT@Void@MnO2/S composite structures is reported. Benefiting from p‐CNTs and sponge‐like MnO2 nanoflake film, p‐CNT@Void@MnO2/S provides highly efficient pathways for the fast electron/ion transfer, fixes sulfur and Li2S aggregation efficiently, and prevents polysulfide dissolution during cycling. Besides, the additional void inside p‐CNT@Void@MnO2/S composite structure provides sufficient free space for the expansion of encapsulated sulfur nanoparticles. The special material composition and structural design of p‐CNT@Void@MnO2/S composite structure with a high sulfur content endow the composite high capacity, high Coulombic efficiency, and an excellent cycling stability. The capacity of p‐CNT@Void@MnO2/S electrode is ≈599.1 mA h g−1 for the fourth cycle and ≈526.1 mA h g−1 after 100 cycles, corresponding to a capacity retention of ≈87.8% at a high current density of 1.0 C.