Na^＋ doped sample Li0.95Na0.05FePO4 was prepared through solid state method. Structure characterization shows Na^＋ is successfully introduced into the LiFePO4 matrix. Scanning electron microscopy shows the particle size mainly ranges in 1-3 μm. X-ray diffraction Rietveld refinement demonstrates lattice distortion with an increased cell volume. As one cathode material, it has a discharge capacity of 150 mAh/g at 0.1 C rate. The material exhibits a capacity of 109 and 107 mAh/g at 5 and 7.5 C respectively. When cycled at 1 and 5 C, the material retains 84% （after 1000 cycles） and 86% （after 350 cycles） of the initial discharge capacity respectively indicating excellent structure stability and cycling performance. Na^＋ doping enhances the electrochemical activity especially the cycle performance effectively.
