Lithium–sulfur (Li–S) batteries have arousing interest because of their high theoretical energy density. However, they often suffer from sluggish conversion of lithium polysulfides (LiPS) during the charge/discharge process. Single nickel (Ni) atoms on nitrogen‐doped graphene (Ni@NG) with Ni–N4 structure are prepared and introduced to modify the separators of Li–S batteries. The oxidized Ni sites of the Ni–N4 structure act as polysulfide traps, efficiently accommodating polysulfide ion electrons by forming strong Sx 2−⋅⋅⋅NiN bonding. Additionally, charge transfer between the LiPS and oxidized Ni sites endows the LiPS on Ni@NG with low free energy and decomposition energy barrier in an electrochemical process, accelerating the kinetic conversion of LiPS during the charge/discharge process. Furthermore, the large binding energy of LiPS on Ni@NG also shows its ability to immobilize the LiPS and further suppresses the undesirable shuttle effect. Therefore, a Li–S battery based on a Ni@NG modified separator exhibits excellent rate performance and stable cycling life with only 0.06% capacity decay per cycle. It affords fresh insights for developing single‐atom catalysts to accelerate the kinetic conversion of LiPS for highly stable Li–S batteries. Single Ni atoms on nitrogen‐doped graphene with a unique Ni–N4 structure are used to modify the separator of a lithium–sulfur battery to improve its electrochemical performance. The oxidized Ni state of the Ni–N4 structure not only serves as an active site for immobilizing lithium polysulfides, but also accelerates their kinetic conversion via electrocatalysis.