Well-shaped and uniformly dispersed LiFePO4 nanorods with a length of 400–500 nm and a diameter of about 100 nm, are obtained with participation of a proper amount of anion surfactant sodium dodecyl sulfonate (SDS) without any further heating as a post-treatment. The surfactant acts as a self-assembling supermolecular template, which stimulated the crystallization of LiFePO4 and directed the nanoparticles growing into nanorods between bilayers of surfactant (BOS). LiFePO4 nanorods with the reducing crystal size along the b axis shorten the diffusion distance of Li+ extraction/insertion, and thus improve the electrochemical properties of LiFePO4 nanorods. Such prepared LiFePO4 nanorods exhibited excellent specific capacity and high rate capability with discharge capacity of 151 mAh/g, 122 mAh/g and 95 mAh/g at 0.1 C, 1 C and 5 C, respectively. Such excellent performance of LiFePO4 nanorods is supposed to be ascribed to the fast Li+ diffusion velocity from reduced crystal size along the b axis and the well electrochemical conductivity. The structure, morphology and electrochemical performance of the samples were characterized by XRD, FE-SEM, HRTEM, charge/discharge tests, and EIS (electrochemical impedance spectra).