Lithium–sulfur (Li–S) batteries, although a promising candidate of next‐generation energy storage devices, are hindered by some bottlenecks in their roadmap toward commercialization. The key challenges include solving the issues such as low utilization of active materials, poor cyclic stability, poor rate performance, and unsatisfactory Coulombic efficiency due to the inherent poor electrical and ionic conductivity of sulfur and its discharged products (e.g., Li₂S₂ and Li₂S), dissolution and migration of polysulfide ions in the electrolyte, unstable solid electrolyte interphase and dendritic growth on anodes, and volume change in both cathodes and anodes. Owing to the high specific surface area, pore volume, low density, good chemical stability, and particularly multimodal pore sizes, hierarchical porous carbon (HPC) materials have received considerable attention for circumventing the above problems in Li–S batteries. Herein, recent progress made in the synthetic methods and deployment of HPC materials for various components including sulfur cathodes, separators and interlayers, and lithium anodes in Li–S batteries is presented and summarized. More importantly, the correlation between the structures (pore volume, specific surface area, degree of pores, and heteroatom‐doping) of HPC and the electrochemical performances of Li–S batteries is elaborated. Finally, a discussion on the challenges and future perspectives associated with HPCs for Li–S batteries is provided.