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Abstract The rational synergy of chemical composition and spatial nanostructures of electrode materials play important roles in high‐performance energy storage devices. Here, we designed pea‐like MoS2@NiS1.03–carbon hollow nanofibers using a simple electrospinning and thermal treatment method. The hierarchical hollow nanofiber is composed of a nitrogen‐doped carbon‐coated NiS1.03 tube wall, in which pea‐like uniformly discrete MoS2 nanoparticles are enclosed. As a sodium‐ion battery electrode material, the MoS2@NiS1.03–carbon hollow nanofibers have abundant diphasic heterointerfaces, a conductive network, and appropriate volume variation‐buffering spaces, which can facilitate ion diffusion kinetics, shorten the diffusion path of electrons/ion, and buffer volume expansion during Na+ insertion/extraction. It shows outstanding rate capacity and long‐cycle performance in a sodium‐ion battery. This heterogeneous hollow nanoarchitectures designing enlightens an efficacious strategy to boost the capacity and long‐life stability of sodium storage performance of electrode materials.