The rational design of sulfur barrier/host materials plays essential roles in developing high-performance lithium-sulfur (Li-S) batteries. Herein, we developed a hierarchically fibrous framework to establish a conductive, adsorptive, and catalytic barrier toward inhibition on polysulfide shuttling and enhancement in Li-S battery performance. The weaving carbonaceous scaffold with vertically-rooted carbon nanofiber (CNF) tentacles facilitates both short- and long-range electrical conduction as well as efficient exposure of active sites, while the multiple adsorptive and catalytic sites enable strong sulfur confinement and expedited sulfur conversion, thus contributing to a fast and durable sulfur electrochemistry. Attributed to these favorable features, Li-S cells based on the as-developed interlayer achieve excellent cyclability with minimum capacity fading rate of 0.018% over 1000 cycles, high rate capability up to 3 C, and decent performance under high raised sulfur loading up to 8 mg cm−2.