With the advent of foldable and wearable electronic devices, flexible sodium ion batteries are being rapidly developed as one of the most appealing power sources. Herein, a flexible Na 3.5 Fe 2.5 (PO 4 ) 1.5 P 2 O 7 /C nanofiber membrane is prepared for application as the cathode of SIBs. Benefited from its excellent electronic conductivity and fast Na + migration, the flexible cathode delivers a high reversible capacity of 83.9 mAh·g –1 and initial Coulombic efficiency of 96.0% at 0.2 C, outstanding rate performance (50 mAh·g –1 at 10 C), and superior cycling stability (93.5% capacity retention over 300 cycles at 0.2 C), based on the membrane mass. Furthermore, the Na 3.5 Fe 2.5 (PO 4 ) 1.5 P 2 O 7 /C cathode exhibits stable cycling with capacity retention of 82.3% after 1500 cycles at 3 C. The reversible Na + intercalation/deintercalation and Fe 2+ /Fe 3+ transformation have been demonstrated by in situ X-ray diffraction and ex situ X-ray photoelectron spectroscopy, respectively. Meanwhile, after HCl etching and annealing, a flexible carbon nanofiber membrane is derived and applied as the anode of SIBs. A coin-type full cell coupling the flexible Na 3.5 Fe 2.5 (PO 4 ) 1.5 P 2 O 7 /C cathode and the flexible carbon anode achieves 90.2% capacity retention after 1500 cycles at 1 C. Furthermore, a foldable full-cell prototype validates the potential of the electrospun flexible nanofiber membrane electrodes for flexible SIBs.