NaVPO 4 F has received a great deal of attention as cathode material for Na‐ion batteries due to its high theoretical capacity (143 mA h g −1 ), high voltage platform, and structural stability. Novel NaVPO 4 F/C nanofibers are successfully prepared via a feasible electrospinning method and subsequent heat treatment as self‐standing cathode for Na‐ion batteries. Based on the morphological and microstructural characterization, it can be seen that the NaVPO 4 F/C nanofibers are smooth and continuous with NaVPO 4 F nanoparticles (≈6 nm) embedded in porous carbon matrix. For Na‐storage, this electrode exhibits extraordinary electrochemical performance: a high capacity (126.3 mA h g −1 at 1 C), a superior rate capability (61.2 mA h g −1 at 50 C), and ultralong cyclability (96.5% capacity retention after 1000 cycles at 2 C). 1D NaVPO 4 F/C nanofibers that interlink into 3D conductive network improve the conductivity of NaVPO 4 F, and effectively restrain the aggregation of NaVPO 4 F particles during charge/discharge process, leading to the high performance.