LAUSR

Seeking an optimal catalyst to accelerate conversion reaction kinetics of room‐temperature sodium–sulfur (RT Na–S) batteries is crucial for improving their electrochemical performance and promoting the practical applications. Herein, theoretical calculations of interfacial interactions of catalysts and polysulfides in terms of the surface adsorption state, interfacial ions migration, and electronic concentration around the Fermi level are systematically proposed as guiding principles of catalyst selection for RT Na–S batteries. As a case, MoN catalyst is accurately selected from transition metal nitrides with different d orbital electrons, and for experiment, it is introduced into the carbon nanofibers as a dual‐functioning host (MoN@CNFs). The MoN@CNFs can effectively anchor polysulfides and accelerate their conversion reaction. In addition, for the sodium anode, the MoN@CNFs can also induce uniform deposition of Na and inhibit dendrite growth, which are supported by in situ characterizations and finite element simulation technique. As a result, the as‐prepared RT Na–S battery displays high reversible capacity of 990 mAh g–1 at 0.2 A g–1 after 100 cycles and long lifespan over 1500 cycles at 2 A g–1. Even with high S loading of 5 mg cm–2, the RT Na–S battery still exhibits a high areal capacity of 2.5 mAh cm–2.