A three-dimensional (3D) hierarchical porous graphene macrostructure coupled with uniformly distributed α-Fe2O3 nano-particles (denoted Fe-PGM) was designed as a sulfur host in a lithium-sulfur battery, and was prepared by a hydrothermal method. In this hybrid structure, the α-Fe2O3 nano-particles are proved to not only strongly interact with the polysulfides, but more importantly, chemically promote their transformation to insoluble species during the charge/discharge process, working as chemical barriers for the shuttling of the lithium polysulfides (LiPSs). Therefore, together with 3D hierarchical porous structure facilitating fast electron/ion transfer, Fe-PGM as a sulfur host in a cathode contributes to a high rate performance (565 mAh g−1 at a high rate of 5C relative to 1571 mAh g−1 at 0.3C) as well as long cyclic stability (an ultralow capacity fading rate of 0.049% per cycle over 1000 cycles at the high current rate of 5C).