Carbon coated triclinic LiVPO4F samples are synthesized by annealing the precursor obtained through a soft chemical route with mechanical activation assist. The V(+5) is reduced to V(+3) by oxalic acid dehydrate during ball milling process, and green slurry of amorphous Li-V-PO4-F is obtained. When the temperature rises to 550 degrees C, the precursor starts crystallizing and good crystal of pure-phase LiVPO4F can be obtained at 550-650 degrees C. But Li3V2(PO4)(3) impurity is observed in samples fired at temperature above 700 degrees C because of the volatilization of HF gas in the presence of moisture at high temperature. Charge-discharge tests show that the sample sintered at 700 degrees C exhibits the best electrochemical performance, delivering the initial discharge capacity of 136 at 0.1 C rate and 123 mAh g(-1) at 1 C rate. Even at 5 C rate, the discharge capacity remains 107 mAhg(-1) and keeps 95.3% after 100 cycles. EIS analysis shows that it possesses smaller impedance than other samples. The apparent chemical coefficient of lithium ions in the prepared sample is evaluated by cyclic voltammetry. Crown Copyright (C) 2012 Published by Elsevier Ltd. All rights reserved.