Traditionally polyvinylidene fluoride membranes have been used in applications such as membrane distillation, wastewater treatment, desalination and separator fabrication. Within this work we demonstrate that a novel carbon nanofiber/polyvinylidene fluoride (CNF/PVDF) composite membrane can be used as an interlayer for LithiumSulfur (LiS) batteries yielding both high capacity and long cycling life. This PVDF membrane is shown to effectively separate dissolved lithium polysulfide with the high electronic conductivity CNF not only reducing the internal resistance in the sulfur cathode but also helping immobilize the polysulfide through its abundant nanospaces. The resulting LiS battery assembled with the CNF/PVDF composite membrane effectively solves the polysulfide permeation problem and exhibits excellent electrochemical performance. It is further shown that the CNF/PVDF electrode has an excellent cycling stability and retains a capacity of 768.6 mAh g−1 with a coulombic efficiency above 99% over 200 cycles at 0.5C, which is more than twice that of a cell without CNF/PVDF (374 mAh g−1). In addition, the low-cost raw materials and the simple preparation process of CNF/PVDF composite membrane is also amenable for industrial production.