In summary, we demonstrated an effective strategy to fabricate a-VONs as an electrode material for the lithium storage. The 1D a-VONs electrode shows the stable discharge capacity of 1425 mAhg−1 at 37 mAg−1 of constant current density and reversible specific capacity ∼945 mAhg−1 without any noticeable fading after 50 cycles at 74 mAg−1. These superior electrochemical properties reveal that the a-VONs exhibit the exceptional lithium storage performance with high reversible capacity and excellent rate capability. These results are attributed to the structural modulation and high electrical conductivity due to the aging for two years. This study on a-VONs used as lithium storage materials demonstrate that the a-VONs can serve as a promising anode material for LIBs and it can be readily adapted to fabricate other high performance electrodes with layer structure.