Tavorite-structured LiFePO4F is synthesized by solid-state reaction and characterized by Rietveld refined X-ray diffraction, scanning electron microscopy, BET surface area, IR and Raman spectroscopy techniques. The ionic conductivity (σ ionic) of LiFePO4F estimated using impedance analysis at 27°C and at 50°C are 0.6(±0.1)×10−7 and 5.4(±0.1)×10−7 Scm−1, respectively, with an energy of activation (E a)=0.75eV. Its electrochemical behavior were examined by galvanostatic charge–discharge cycling up to 100 cycles, cyclic voltammetry (CV) and electrochemical impedance spectroscopy using Li-metal as the counter and reference electrode, at 0.1C rate in the voltage range, 1.5–4V. LiFePO4F delivers an initial discharge capacity of 115(±3)mAhg−1 which increases to 119(±3)mAhg−1 at the 20th cycle. The capacity degrades slowly thereafter over 100 cycles, with a capacity loss of 19%. CV data show a clear indication of the Fe3+/2+ redox couple at 3.3–2.6V that involves a two-phase reaction. Electrochemical impedance spectra measured at various voltages at selected cycles were fitted to an equivalent circuit and the variation of impedance parameters interpreted.