Amorphous structure, possessing vast preponderances for boosting the application of lithium-ion batteries (LIBs), has drawn considerable attention as an elegant electrode structure. However, due to its thermal instability, amorphous transition-metal vanadates lack of exploration. In this work, we firstly report the fabrication of Ni3V2O8 amorphous wire encapsulated in crystalline tube nanostructure (NV-aWcT) by single spinneret electrospinning with subsequent heat treatment. The formation of this unique nanostructure is ascribed to shell heat transfer retardation by tuning the pyrolysis balance between “surface locking” and “inward migration” during the calcination process. Benefit from the collective characteristics of interior amorphous wire and outer tubular shell, NV-aWcT possesses mesoporosity, void spaces, defective sites and high surface areas, realizing superior electrochemical performance with high specific capacity, outstanding cycling stability, and superior rate capability (962mAhg–1 at 300mAg–1 after 300 cycles).