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 Zn2 V2 O7 (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.