Abstract: Lithium-sulfur (LiS) batteries exhibit great potential as the next-generation energy storage techniques. Application of catalyst is widely adopted to accelerate the redox kinetics of polysulfide conversion reactions and improve battery performance. Although significant attention has been devoted to seeking new catalysts, the problem of catalyst passivation remains underexplored. Herein, we find that metal-N coordination has a previously overlooked role in preventing the catalyst passivation. In the case of nickel, the Ni catalyst reacts with S8 to produce NiSx compounds on the surface, leading to catalyst passivation and slow the kinetics of LiPSs conversion. In contrast, when Ni is coordinated with N (typically NiN4), S8 remains stable on the surface. The NiN4 exhibits excellent resistance to passivation and rapid kinetics of LiPSs conversion. Consequently, the sulfur cathode with NiN4 exhibits a high rate capability of 604.11 mAhg1 at 3 C and maintains a low capacity decay rate of 0.046% per cycle over 1000 cycles at 2 C. Furthermore, preventing S passivation in MN coordination applies not only to NiN4 but also to various coordination numbers and transition metals. This study reveals a new aspect of metal-N coordination in inhibiting catalyst passivation, improving our understanding of catalysts in LiS batteries.