The abundance of sodium resources indicates the potential of sodium-ion batteries as emerging energy storage devices. However, the practical application of sodium-ion batteries is hindered by the limited electrochemical performance of electrode materials, especially at the anode side. Here, we identify alkaline earth metal vanadates as promising anodes for sodium-ion batteries. The prepared calcium vanadate nanowires possess intrinsically high electronic conductivity (> 100 S cm-1), small volume change (< 10%), and a self-preserving effect, which results in a superior cycling and rate performance and an applicable reversible capacity (> 300 mAh g-1), with an average voltage of ∼1.0 V. The specific sodium-storage mechanism, beyond the conventional intercalation or conversion reaction, is demonstrated through in situ and ex situ characterizations and theoretical calculations. This work explores alkaline earth metal vanadates for sodium-ion battery anodes and may open a direction for energy storage.The development of suitable anode materials is essential to advance sodium-ion battery technologies. Here the authors report that alkaline earth metal vanadates are promising candidates due to the favorable electrochemical properties and interesting sodium-storage mechanism.