In this work, a novel system of ethylene glycol/water (EG/W) was employed to synthesize LiFePO4, in which dodecyl benzene sulphonic acid sodium (SDBS) was used as soft template to control particle morphology. The samples were characterized by X-ray diffractometer (XRD), field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDX). The LiFePO4 sample obtained by the reported method displays interesting hierarchical nanostructure (i.e. nanodendrites), which was constructed by nanorods of 3-5 mu m in length and similar to 50 nm in diameter. The EG/W ratio, amount of SOBS added, hydrothermal temperature and duration played important roles in the assembly of the hierarchical nanostructures. A formation mechanism was proposed and experimentally verified. It is concluded that the nanodendrites were formed due to the end-to-end self-assembly of nanorods. Compared to previously reported methods, the reported approach shows obvious advantages of one-step synthesis, environmental friendliness and low cost, to name a few. The nanodendrites as a cathode material have a higher capacity, compared with the other samples. (C) 2010 Elsevier B.V. All rights reserved.