The carbon microtubules core structure LiFePO4 is synthesized using a cotton fiber template-assisted method. The crystalline structure and morphology of the product is characterized by X-ray diffraction and field emission scanning electron microscopy. The charge-discharge kinetics of the LiFePO4 electrode is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The result shows that the well-crystallized carbon microtubules core structure LiFePO4 is successfully synthesized. The as-synthesized material exhibits a high initial discharge capacity of 167 mAh g-1 at 0.2 C rate. The material also shows good high-rate discharge performance and cycling stability, about 127 mAh g-1 and 94.7 % capacity retention after 100 cycles even at 5.0 C rate.