With the development of technology, higher demands are placed on the performance of energy storage devices. The traditional lithium ion batteries have approached its peak capacity, which are unable to meet the ever-increasing demands for its energy density. Lithium-sulfur batteries are endowed with an excellent theoretical energy density (2600 Wh·kg-1), which is promising to replace the traditional lithium ion batteries as the next generation energy storage devices with high energy density. However, the severe shuttle effect of the polysulfides, sluggish kinetics of sulfur speices-redox reactions and the enormous volume change (~80%) of sulfur cathode over the charge-discharge cycles are main factors restricting the development of lithium-sulfur batteries. Due to the superior nanostructure, electrospun nanofiber materials commonly show some unique characteristics which can simultaneously resolve these problems even at the harsh conditions of high sulfur loading and lean electrolyte. This review introduces recent progress and structure design on electrospun nanofiber for the cathode, separator, and interlayer aspects in lithium-sulfur batteries. The impact of the material properties and structure on lithium-sulfur batteries performance are analyzed. The research and development directions of electrospun nanofibers for various parts of lithium-sulfur batteries are proposed.