Lithium–sulfur batteries have been researched extensively because of their high energy density and low price. However, the poor conductivity of sulfur, the shuttle effect of polysulfide, the slow redox kinetics of sulfur species, and the significant volume expansion and contraction during charging and discharging have hindered the commercial application of lithium–sulfur batteries. In this study, a simple, scalable, and cost-effective strategy was developed to control the balance of the porosity, specific surface area, graphitization, heteroatom co-doping, and polar-polar interactions of a biomass carbon source. With this strategy, multifunctional porous carbon materials with three-dimensional network structures were prepared to serve as sulfur-loading hosts with high specific surface area, strong adsorption activity, and good conductivity. Moreover, the optimal porous carbon material was directly coated on a commercial separator, and the modified separator was found to further improve the electrochemical performance of a lithium–sulfur battery. As a result, for the battery with GPCS-3 as cathode electrode and modified separator as separator, the initial discharge capacity at 1.0C is 926.2 mAh g−1. After 300 cycles, the discharge capacity is 712.7 mAh g−1, and the average capacity decay is only 0.077 % per cycle. Since the three-dimensional network structure material exhibits good performance as a sulfur-loading host as well as the ability to effectively modify a separator, this study provides a valuable strategy for the fabrication of high energy density lithium–sulfur batteries.