Hollow bismuth ferrite nanofibers were fabricated via simple electrospinning process, and the storage properties of Na-ions were investigated by atmospheric pressure X-ray photoelectron spectrum (APXPS) and Synchrotron Radiation. The results show that the hollow bismuth ferrite nanotubes demonstrate impressive sodium storage properties and good cycling stability that the specific capacity can exceed 500 mA h g(-1) and the cycle number reaches several hundred cycles. The graphene-coated bismuth ferrite nanotubes exhibit a specific capacity of 600 mAh g(-1) and a 89% capacity retention after 200 cycles. The present strategy can be a significant step to fabricate hollow perovskite oxides and serve as sodium ion batteries.