In this work, LiFePO4/C composites were prepared in hydrothermal system by using iron gluconate as iron source, and two feeding sequences during the preparation were comparatively studied. The morphology, crystal structure and charge-discharge performance of the prepared samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and galvanostatic charge-discharge testing. The results showed that the feeding sequences and iron gluconate seriously affected the microstructures and electrochemical properties of the resulting LiFePO4 cathodes in lithium ion batteries. The spindle-shaped LiFePO4 with hierarchical microporous structure self-assembled by nanoparticles has been successfully synthesized by synthesis route B. In addition, the cell performance of the synthesized LiFePO4 by synthesis route B was better than that of LiFePO4 by synthesis route A. Specially at high rates, the superior rate performance of the spindle-shaped LiFePO4/C microstructure (LFP/C-B) was revealed. And special reversible capacities of similar to 118 and similar to 95 mAh g(-1) were obtained at rates of 2 C and 5 C, comparing to similar to 96 and similar to 68 mAh g(-1) for LFP/C-A. (C) 2011 Elsevier Ltd. All rights reserved.