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Transition-metal selenides have been recognized as a class of promising anode materials for sodium-ion batteries (SIBs) on account of their high capacity. Nevertheless, the sluggish conversion kinetics and rapid capacity decay caused by insufficient conductivity and volume change restrain their applications. Herein, hollow heterostructured bimetallic selenides embedded in an N-doped carbon nanoframework (H-CoSe 2 /ZnSe@NC) were prepared via a facile template-engaged method. Benefiting from the rich defect at the phase boundary of the CoSe 2 /ZnSe heterostructure, pre-reserved cavity, and enhanced structure rigidity, the abovementioned issues are resolved at once, and the accelerated charge transportation kinetics traced by spectroscopy techniques and theoretical calculations certify the interface effect in the capacity release. In addition, ex situ X-ray photoelectron spectroscopy, X-ray diffraction, and high-resolution transmission electron microscopy all confirm the high-reversible electrochemical conversion mechanism in H-CoSe 2 /ZnSe@NC. Together with a reasonable structural architecture and the highly reversible conversion reaction, H-CoSe 2 /ZnSe@NC displays a prominent rate capacity (244.8 mA h g −1 at 10 A g −1 ) as well as an ultralong lifespan (10,000 cycles at 10 A g −1 ), highlighting the significance of structure control in fabricating high-performance anodes for SIBs.

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