AbstractMetallic conductive 1T phase molybdenum sulfide (MoS₂) has been identified as promising anode for sodium ion (Na⁺) batteries, but its metastable feature makes it difficult to obtain and its restacking during the charge/discharge processing result in part capacity reversibility. Herein, a synergetic effect of atomic‐interface engineering is employed for constructing 2H‐MoS₂ layers assembled on single atomically dispersed Fe−N−C (SA Fe−N−C) anode material that boosts its reversible capacity. The work‐function‐driven‐electron transfer occurs from SA Fe−N−C to 2H‐MoS₂ via the Fe−S bonds, which enhances the adsorption of Na⁺ by 2H‐MoS₂, and lays the foundation for the sodiation process. A phase transfer from 2H to 1T/2H MoS₂ with the ferromagnetic spin‐polarization of SA Fe−N−C occurs during the sodiation/desodiation process, which significantly enhances the Na⁺ storage kinetics, and thus the 1T/2H MoS₂/SA Fe−N−C display a high electronic conductivity and a fast Na⁺ diffusion rate.