Rechargeable lithium-sulfur battery with a high theoretical energy density attracts intense attention, but it still often suffers from poor cyclability. Herein, a hierarchical porous carbon/graphene hybrid is designed to host sulfur for Li–S battery. The batteries exhibit good performances including a specific capacity of 1178 mA h g−1 after 70 cycles at 0.2C, a stable reversible capacity of 400 mA h g−1 after 600 cycles at 1.0C (80% retention). Extensive characterizations including adsorption-desorption isotherms, XRD, Raman spectroscopy, HAADF-STEM combining with soft XAS study the relationship between the structure and the performance of as-synthesized cathode material. The synergistic effect of graphene and hierarchical porous carbon provides the pathway of the electron and Li+ ingress/egress to react with the confined sulfur clusters, retard the loss of the polysulfide anions from the cathode and suppress the shuttle effect during long-term cycling process.