Lithium-sulfur (Li-S) batteries are regarded as a potential next-generation energy storage system but they are hampered by low active-material utilization, polysulfide shuttling, and rapid capacity fade. We present here the use of lightweight boron- and nitrogen-doped reduced graphene oxide (B-rGO, N-rGO) coated separators to suppress polysulfide diffusion and enhance active material utilization at high sulfur contents. B-rGO and N-rGO are synthesized through a facile modified Hummer's method involving the exfoliation of graphite sheets. Upon reduction, the carbon forms valuable interlayers with dynamic spacings for polysulfide trapping. Freeze-drying is utilized to preserve the structure of the pillow-like carbon, which is then slurry-coated onto a separator and placed against a sulfur cathode. The advantages of boron and nitrogen and their affinity towards polysulfides is compared while noting the lighter carbon coatings with good electrochemical stability. The cells attain a loading of 4.0 mg cm−2 with a high sulfur content of 66.5 ± 0.5 wt % on including the weight of the coatings. After a long cycle life of 400 cycles, N-rGO and B-rGO are still able to maintain a specific capacity of, respectively, 430 mA h g−1 and 367 mA h g−1.