Hierarchical mesoporous carbon was studied as a key material for enhancing sulfur utilization in Li−S batteries. Commonly, thermal sulfur infiltration into mesoporous carbon was a representative method for S−C composites; however, these had some problems such as pore blocking or nonuniform deposition of sulfur. Electrochemical sulfur impregnation without chemical or thermal infiltration reduced the preprocess time and enabled efficient polysulfide diffusion into the carbon pores. As the soluble polysulfides are smaller and more mobile than solid‐state sulfur, they could be physically or chemically adsorbed into the pores of the carbon additives. This approach enhanced the cycle stability and rate performance of the batteries. This study will provide an efficient and economic use of porous carbons in the Li−S battery field.