Cationic surfactant cetyltrimethylammonium bromide (CTAB) was used as template to prepare porous structure LiFePO4/C composite by the template method. The porous structure LiFePO4/C composites were characterized using X-ray diffraction (XRD). scanning electron microscope (SEM), transition electron microscopy (TEM), high voltage electron microscopy (HVEM), and nitrogen adsorption-desorption test. The structures and electrochemical performances of the samples calcined at different calcination times at 700 degrees C were studied. The results indicate that the porous structure LiFePO4/C composite prepared at 700 degrees C for 24 h exhibited the best electrochemical performance, the discharge capacity is up to 152.1 mAh g(-1) at 0.1 C rate. Compared with nano-sized LiFePO4/C composite without template, porous structure LiFePO4/C could dramatically improve the rate capability because of its higher specific surface area and more channels for fast lithium ion diffusion. (C) 2012 Elsevier B.V. All rights reserved.