This Olivine LiFe 1-xCa xPO 4/C composites (x=0 - 0.014) were synthesized by a solid-state method using sebasic acid as a carbon source. The structure and electrochemical properties of the LiFe 1-xCa xPO 4/C compounds were studied. The X-ray diffractometer (XRD) results indicated that Ca 2+ doping did not affect the structure of the samples, but the unit cell volume of doped sample are slightly increased. Electrochemical measurements showed that the LiFe 0.99Ca 0.01PO 4/C composite delivered a discharge capacity of 149 mAh g -1 at a 0.2 C-rate between 4.0 and 2.8 V, probably due to the significant improvement of electronic conductivity and Li + ion diffusion. Besides, the cell can sustain a 20 C-rate, and this rate capability is equivalent to charge or discharge in 3 min.