Lithium–sulfur (Li–S) batteries have a distinct advantage over other rechargeable battery systems since their high specific energy and low cost. However, the diffusion of polysulfides from cathode to anode leads to poor electrochemical stability of Li–S batteries, which is a main factor that restricts their further development. Herein, for the first time we present a separator with nitrogen-doped porous hollow carbon sphere (NHC) coating, with which Li–S cells enormously improve the utilization of active material and enhance excellent electrochemical performance. An initial discharge capacity of 1656 mAh g−1 (0.2 C) and a low fading rate of 0.11% per cycle within 500 cycles (1 C) are achieved, which ascribe to the chemical and physical adsorption properties of porous and nitrogen-doped NHCs. The NHC-decorated separator is of low cost and can effectively improve energy density of Li–S cells, exhibiting potential for further development of Li–S batteries.