Using excellent kinetic transport graphitized carbon nanofibers network to construct free-standing V2O5-based electrode is an effective approach to develop high-performance lithium ion batteries. Herein, we successfully prepare graphitized carbon nanofibers by combining the electrospinning and the catalytic effect of iron oxide, and the conductance of graphitized carbon nanofibers is increased by 5 × 10 4 times compared to the amorphous carbon. Through hydrothermal method, the V2O5 nanosheets can be anchored on the surface of graphitized carbon nanofibers, forming a flexible and free-standing composite electrode, which can be directly used as cathode electrodes with a reversible capacity of 290 mAh g−1 at 0.1 C and a capacity higher than 105 mAh g−1 even at a large current density of 20 C, retaining a capacity of 160 mAh g−1 at 5.0 C even over 700 cycles. This is the first report to synthesize V2O5 nanosheets on graphitized carbon nanofibers prepared by electrospinning to construct a free-standing composite electrode with high rate capability and cycling stability lithium ion storage performances.