Lithium-sulfur batteries are promising battery systems for becoming the next-generation energy storage devices. However, realizing their practical application is greatly challenged by the limitation of exhibiting poor cycling performances owing to the low electrical conductivity of sulfur active material and polysulfide shuttling effects during cycling. To solve these issues, a hybrid structure of reduced graphene oxide and poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) was fabricated and coated onto the surface of the conventional separator using the air-controlled electrospraying method in this work. By applying these separators to the lithium-sulfur batteries, lower polarization ensued and a combination of chemical, physical, and electrostatic interactions mitigated the polysulfide shuttling effect. Hence, using these bi-functional coatings led to high initial capacity and improved cycling performances, resulting from to the higher utilization of active material and less loss of active material. Overall, this investigation demonstrates the potential for this coating material being adopted to improve lithium-sulfur battery technology.