Optimizing charge transfer and alleviating volume expansion in electrode materials are critical to maximize electrochemical performance for energy storage systems. Herein, an atomically thin soft-rigid Co S @MoS core-shell heterostructure with dual cation vacancies at the atomic interface is constructed as a promising anode for high-performance sodium-ion batteries. The dual cation vacancies involving V and V in the heterostructure and the soft MoS shell afford ionic pathways for rapid charge transfer, as well as the rigid Co S core acts as the dominant active component and resists structural deformation during charge/discharge. Electrochemical testing and theoretical calculations demonstrate both excellent Na transfer kinetics and pseudocapacitive behavior. Consequently, the soft-rigid heterostructure delivers extraordinary sodium storage performance (389.7 mA h g after 500 cycles at 5.0 A g ), superior to those of the single-phase counterparts; and the assembled Na V (PO ) ||d-Co S @MoS /S-Gr full cell achieves an energy density of 235.5 Wh kg at 0.5 C. Our finding opens up a new strategy of soft-rigid heterostructure and broadens the horizons of material design in energy storage and conversion. This article is protected by copyright. All rights reserved.