Na2Ti3O7 nanofiber was prepared by using electrospinning and thermal treatment process. It was first time to introduce Na2Ti3O7 nanofiber as anode for sodium-ion batteries. Na2Ti3O7 nanofiber achieved charge capacity as high as 257.8 mAh g−1 at the first cycle. Good rate capability was exhibited on nanofiber-structured Na2Ti3O7.