In this study, Silicon and petroleum pitch were coated on the surface of Si/C fiber manufactured using electrospinning to improve the electrochemical performances. SiO2/PAN fiber was prepared by electrospinning with TEOS and PAN at various ratios dissolved in DMF. The characteristics of carbonization, reduction, and pitch coating processes were investigated for the optimal process of the pitch coated Si/C fiber anode composite. Anode composite prepared with TEOS/PAN = 4/6 (CR-46) after carbonization and reduction process has a capacity of 657 mAh/g. To improve capacity and stability, Si powder and PFO pitch were coated at the surface of CR-46. When the pitch composition was fixed at 10 wt%, it was found that the capacity increased as the weight ratio of silicon increased, but the stability decreased. The pitch coated Si/C fiber composite with 10 wt% silicon has high capacity of 982.4 mAh/g and capacity retention of 86.1%. In the test to evaluate rate performance, the rate capability was 80.2% (5C/0.1C).