Lithium-sulfur (Li-S) batteries have attracted great interest owing to their high energy density. However, shuttling of polysulfides deteriorates the electro-chemical performance of Li-S batteries and prevents their practical applications. Placing a conductive and porous interlayer structure between the cathode and the separator limits the shuttling effect and improves the cycling performance. Here, porous carbon microfibers are fabricated via a fast, safe and cost-effective centrifugal spinning approach and the resultant centrifugally spun porous carbon microfibers (CS-PCMFs) are evaluated for use as an interlayer in Li-S batteries. The highly porous fibrous structure is observed from SEM and TEM images, and a high initial discharge capacity of 1485 mAh g(-1) is achieved. A high reversible capacity of 615 mAh g(-1) is reached after 200 cycles at 0.2 C. In addition, the cell with CS-PCMF interlayer has low cell resistance of 25 O, whereas that of Li-S cell without interlayer is 55 O. Owing to the low cell resistance, the cell with CS-PCMF interlayer delivers the reversible capacity of around 600 mAh g(-1) at 1 C, while the cell without interlayer exhibits a lower capacity of 250 mAh g(-1). Therefore, this work provides a new approach for designing highly porous carbon microfiber interlayer for Li-S batteries with exceptional electrochemical performance.