In this paper, twelve LiFePO4 samples with different size and shape have been successfully synthesized in Water/ethylene glycol solution. The morphology of the as-prepared LiFePO4 can be controlled by the addition sequence of the precursors and the ratio of W/EG. LiFePO4 nano- and microcrystals can be prepared by the traditional addition sequence Fe-PO4-Li and Li-PO4-Fe by adjusting the W/EG ratio. The new precursor separated hydrothermal synthesis (PSHS) method were conducted by packing the FeSO4 solution in polymer bag and separated with Li3PO4 precipitation before the hydrothermal treatment. The PSHS method obtained samples were all nanoscaled. The XRD, SEM, TEM and electrochemical testing were used to determine the structural and morphology effects on the electrochemical properties of the materials. (C) 2015 Elsevier B.V. All rights reserved.