Lithium-sulfur (Li-S) batteries have a lot of potential to be used as next-generation batteries because of its advantages in high specific energy density, low cost of raw materials, and environmental friendliness. There has been a lot of work done on developing new Li-S cathode materials to overcome their limitations, but less has been done on improving separators, which can have a significant impact on ion diffusion and other battery safety issue.In this work, electrospinning is used to fabricate polyvinylidene fluoride (PVDF)/ceramic hybrid coating on Celgard separators. The effect of coating layer on separator’s thermal stability, physical properties and electrochemical performance is investigated. The results clearly showed that the separator with PVDF/ceramic hybrid coating has wonderful thermal stability, good wettability, and high uptake of liquid electrolyte. The innovative nature of the work lies in tailoring the electrospinning parameters, morphology, and thickness of the ceramic to improve electrochemical, and cell performance, and coating the polymer/ceramic blend on Celgard separator. Coin cell tests with the PVDF/ceramic hybrid coated separator also show excellent stable cycle performance. Furthermore, effective fabrication of free-standing non-woven hybrid PVDF/ceramic separators was conducted. Due to high ionic conductivity through the fibrous structure and excellent electrolyte interactions with ceramics, these separators display improved cycling performance at high charge/discharge rates in Li-S cells.