Non-woven nickel/carbon nanofibers (NW(Ni/C)NFs) are developed using a facile one-pot electrospinning method as a functional interlayer for rechargeable lithium-sulfur (Li-S) batteries. The functional interlayer of NW(Ni/C)NFs is sandwiched between a sulfur cathode and the separator and acts as a shuttle inhibitor to sulfur and polysulfides. Because of the sandwiched structure and the nickel additive, the Li-S cell shows better performance in terms of capacity utilization and reversibility. When the NW(Ni/C)NFs were calcined at 900 °C with 1 g of nickel salt additive, the discharge capacity of the cells was the best, and the initial discharge capacity was 1062 mAh g-1. With 200 charge-discharge cycles at 1 C, the discharge capacity of the cells remained above 910 mAh g-1, which is about 85.7% of its initial capacity. The improvement to the cells' electrochemical performance is attributed to the 3D architecture of the NW(Ni/C)NFs as a functional interlayer and to the appropriate amount of nickel addition. This provides a good conductive network with structural stability and the migrating polysulfide reduces the "shuttling phenomenon" during the charge-discharge processes.