Lithium-Sulfur (Li-S) batteries, the most promising next-generation batteries for their high theoretical capacity, are still hindered by several obstacles mainly due to the effect of polysulfide shuttle. Recently, considerable progress has been made to improve the specific capacity and cycling life of the Li-S batteries, but most demonstrations are typically based on thin electrode with limited areal sulfur loading. Herein, we demonstrate a Li-S battery with electrospun carbon nanofiber/reduced graphene oxide (CNF/rGO) as the binder-free and self-standing host for lithium polysulfide-containing liquid active materials in the cathode. The matrix of intertwined long CNF networks with uniformly distributed rGO pieces promotes the long-range high-rate charge transfers in three dimensions, and provides sufficient porous spaces for polysulfide uptake. Plus the mechanical flexibility of the CNF/rGO membrane, thick electrode with high areal sulfur loading (20.3mg/cm2) and high areal specific capacity (15.5mAh/cm2) is demonstrated by a Li-S pouch cell with stable cycling performances.