The effects of fluorine substitution on the electrochemical properties of LiFePO4/C cathode materials were studied. Samples with stoichiometric proportion of LiFe(PO4)(1-x)F-3x/C (x=0.025,0.05, 0.1) were prepared by adding LiF in the starting materials of LiFePO4/C. XRD and XPS analyses indicate that LiF was completely introduced into bulk LiFePO4 structure in LiFe(PO4)(1-x)F-3x/C (x= 0.025, 0.05) samples, while there was still some excess of LiF in LiFe(PO4)(0.9)F-0.3/C sample. The results of electrochemical measurement show that F-substitution can improve the rate capability of these cathode materials. The LiFe(PO4)(0.9)F-0.3/C sample showed the best high rate performance. Its discharge capacity at 10 C rate was 110 mAh g(-1) with a discharge voltage plateau of 3.31-3.0 V versus Li/Li+. The LiFe(PO4)(0.9)F-0.3/C sample also showed obviously better cycling life at high temperature than the other samples. (C) 2007 Elsevier B.V. All rights reserved.