© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Applications of room-temperature–sodium sulfur (RT-Na/S) batteries are currently impeded by the insulating nature of sulfur, the slow redox kinetics of sulfur with sodium, and the dissolution and migration of sodium polysulfides. Herein, a novel micrometer-sized hierarchical S cathode supported by FeS2 electrocatalyst, which is grown in situ in well-confined carbon nanocage assemblies, is presented. The hierarchical carbon matrix can provide multiple physical entrapment to polysulfides, and the FeS2 nanograins exhibit a low Na-ion diffusion barrier, strong binding energy, and high affinity for sodium polysulfides. Their combination makes it an ideal sulfur host to immobilize the polysulfides and achieve reversible conversion of polysulfides toward Na2S. Importantly, the hierarchical S cathode is suitable for large-scale production via the inexpensive and green spray-drying method. The porous hierarchical S cathode offers a high sulfur content of 65.5 wt%, and can deliver high reversible capacity (524 mAh g−1 over 300 cycles at 0.1 A g−1) and outstanding rate capability (395 mAh g−1 at 1 A g−1 for 850 cycles), holding great promise for both scientific research and real application.