Hollow microstructure always exhibits some special properties in the field of electrochemistry. Here, this study reports the rational design and preparation of TiNb2O7 nanofibers with one dimensional hollow structure via co-electrospinning. The as-electrospun TiNb2O7 hollow nanofibers show high intercalation potential, low charge-charge resistance and fast electrochemical kinetics. The electrochemical results exhibit that the TiNb2O7 hollow nanofibers deliver a reversible capacity of 210.1mAhg−1 after 150 cycles at a current rate of 0.4C, and 158.4mAhg−1 after 900 cycles even at a current rate of 10C with an outstanding capacity retention of 80.6%. The excellent electrochemical performance of nanofibers can be related to the unique morphology of hollow structure. Furthermore, the lithium ions storage mechanism of TiNb2O7 hollow nanofibers is also systematically analyzed, which is related to one two-phase coexistence and two solid-solution processes during the whole charge-discharge cycle. In addition, it is also demonstrated by in situ and ex situ observations that TiNb2O7 hollow nanofibers have outstanding structural stability and electrochemical reversibility. Therefore, the TiNb2O7 hollow nanofibers can be applied as an alternative promising electrode material for the next rechargeable lithium ions batteries.