For lithium‑sulfur batteries (LSBs), some barriers like low conductivity of sulfur, the large irreversible volume change and the “shuttle” issue, hinder its practical application. In this work, Fe-functionalized mesoporous carbonaceous microspheres with high conductivity and intensive chemical adsorption for polar polysulfide species (LiPSs) were successfully synthesized through economical, scalable solvothermal process and pyrolyzing method. Carbon microspheres with Fe/Fe3C components (denoted as CMS900) exhibit high conductivity and significantly enhance the electrochemical reaction kinetics despite 81 wt% sulfur loading. Furthermore, the proper amount surface oxygenic functional groups effectively immobilize sulfur via strong chemical entrapment and suppress the dissolution of LiPSs intermediates during cycling. The CMS900@S has demonstrated a high initial discharge capacity of 1269 mAh g−1 at 0.1C, over 200 cycles with the lowest average capacity fading rate of 0.06% per cycle, which can be treated as an alternative cathode material for LSBs with impressive electrochemical performance.