Lithium–sulfur (Li–S) batteries are expected to be very useful for next-generation transportation and grid storage because of their high energy density and low cost. However, their low active material utilization and poor cycle life limit their practical application. The use of a carbon-coated separator in these batteries serves to inhibit the migration of the lithium polysulfide intermediate and increases the recyclability. We report the extent to which the electrochemical performance of Li–S battery systems depends on the characteristics of the carbon coating of the separator. Carbon-coated separators containing different ratios of carbon black (Super-P) and vapor-grown carbon fibers (VGCFs) were prepared and evaluated in Li–S batteries. The results showed that larger amounts of Super-P on the carbon-coated separator enhanced the electrochemical performance of Li–S batteries; for instance, the pure Super-P coating exhibited the highest discharge capacity (602.1 mAh g−1 at 150 cycles) with a Coulombic efficiency exceeding 95%. Furthermore, the separators with the pure Super-P coating had a smaller pore structure, and hence, limited polysulfide migration, compared to separators containing Super-P/VGCF mixtures. These results indicate that it is necessary to control the porosity of the porous membrane to control the movement of the lithium polysulfide.