Focusing on multifunctional mesoporous carbonaceous materials (MCMs) is one of the hot research topics due to increasing demand in the high-energy-density devices of lithium-sulfur (Li-S) batteries (2600 Wh kg-1). On the premise of applying MCMs as a porous framework to load elemental sulfur, to improve the electronic conductivity of the cathode, and to trap the in situ-formed electrolyte-soluble intermediates of lithium polysulfides (LiPSs), the commercialization of MCMs-based energy storage devices still needs to solve solid/solid and solid/liquid interfacial issues such as the chemical anchoring of the electrically insulating active substances, the sluggish redox kinetics of intermediate LiPSs, and so on. Through the permutation of multifunctional MCMs serving as the primary sulfur-loading carrier of the cathode, as the secondary surface-coating layers of the separator, the cathode, and the anode separately, this Perspective highlights research challenges to clarify a comprehensive high-performance mechanism of MCM-based Li-S batteries and provides new chemical insight for potential application purposes.