With the rapid development of intermittent renewable energy and regional smart grid, lithium-ion batteries (LIBs) are failing to accommodate the growing requirement for large-scale energy storage applications, due to the resource constraints of lithium. [1][2][3] In recent years, sodium-ion batteries (SIBs) have been researched as one of the potential alternatives to LIBs considering the earth abundance and low cost of sodium. [4][5][6] Developing anode materials with stable and fast sodium-ion storage properties is one of the keys to the commercial application of SIBs. [6,7] However, despite the similar working mechanism of SIBs and LIBs, many common anode materials are not suitable for SIBs, while display excellent lithium storage properties in LIBs. [8][9][10] Compared with lithium-ion, sodium has a larger ionic radius and atomic mass, which lead to sluggish reaction kinetics and drastic volume change of anode materials during sodiation/desodiation processes. [4,11] For example, as one of promising mixed transition metal oxides (MTMOs) anode materials for LIBs, metal vanadates usually show outstanding lithium storage performance with high specific capacities Developing nanomaterials with synergistic effects of various structural merits is considered to be an effective strategy to improve the sluggish ion kinetics and severe structural degradation of sodium-ion battery (SIB) anodes. Herein, honeycomb-like amorphous Zn 2 V 2 O 7 (ZVO-AH) nanofibers as SIBs anode material with plentiful defective sites, complex cavities, and good mechanical flexibility are reported. The fabrication strategy relies on the expansive and volatile nature of the organic vanadium source, based on a simple electrospinning with subsequent calcination. Originating from the synergies of amorphous nature and honeycomb-like cavities, ZVO-AH shows increased electrochemical activity, accelerated Na-ion diffusion, and robust structure. Impressively, the ZVO-AH anode delivers superior cycle stability (112% retention at 5 A g −1 after 5000 cycles) and high rate capability (150 mAh g −1 at 10 A g −1 ). The synthetic versatility is able to synergistically promote the practical application of more potential materials in sodium-ion storage. www.advancedsciencenews.com