While the design of a Li₃VO₄ (LVO) anode is severely hindered by its hydrophilicity, here the state-of-the-art Li₃VO₄/C nanoflakes with specific crystalline plane exposure (C@LVO-NFs) are designed and synthesized for the first time via a reverse water-etching strategy. A new interfacial Li-ion storage mechanism is demonstrated via theoretical calculations, which is responsible for the ultra-high capacity of the C@LVO-NFs beyond the theoretical value of LVO (850.8 mA h g⁻¹ at 0.2 A g⁻¹ over 150 cycles). Moreover, the exposed crystal planes of LVO and the interfaces with C are proven to be highly conductive for both Li-ions and electrons, giving rise to superior reaction kinetics. These, together, trigger outstanding high-rate and long-life performance of C@LVO-NFs, which outperform most of the LVO-based anode materials. When cycling at a discharge current of 4.0 A g⁻¹ over 6000 cycles, the C@LVO-NFs could deliver a discharge capacity of 637.7 mA h g⁻¹. The reverse strategy for the synthesis of C@LVO-NFs may be referential for the design of advanced LVO-based electrodes, and the outstanding high-rate performance of the C@LVO-NFs demonstrates great potential toward practical applications.