Polyacrylonitrile carbon nano-fibers is prepared by electrospinning and high temperature carbonization technology. The obtained ES-PAN nano-fibers shows a disordered and porous nanoscale-morphology with larger specific surface area and more exposed active sites. Meanwhile, the porous microstructure provides a fast channel for lithium ion transport. As a result, the ES-PAN electrode shows superior performance as anode materials for lithium ion batteries such as higher capacity, superior rate capability and cycle life. The initial charging capacities of ES-PAN electrode are 404.7, 266.5, 182.9 and 113.8 mAh/g at the rate of 0.2 C, 1C, 3C and 5 C respectively, which are significantly higher than the electrodes of PAN hard carbon (PAN-1000) calcined at 1000 °C (359.8, 197.3, 149.3 and 39.5 mAh/g, respectively) and graphite (329.5, 222.9, 55.5 and 17.7 mAh/g, respectively). After 100 cycles, the charging capacities of ES-PAN electrode can still remain at 375.5, 268.6, 167.3 and 105.0 mAh/g with the capacity retention of 92.8%, 100.7%, 91.5% and 92.3% at the rate of 0.2 C, 1 C, 3 C and 5 C, respectively, which are also much higher than those of PAN-1000 and graphite electrodes. The ES-PAN nanofiber electrodes prepared by electrospinning technology show higher capacity, better rate capability and cycling stability.