LiFePO4 crystallizes in olivine structure. It is a mixed electronic-ionic conductor and has been proposed as an attractive cathode material for Li-ion secondary batteries. The conductivity values increased with increasing the amount of carbon in the LiFePO4/C composites [2]. It is known [3] that in this compound Fe2+ can be oxidized to Fe3+. The material has a high reversible capacity (~160 mAhg-1) and the intercalation potential for Li/Li+ is 3.5 V The redox behavior of the iron in this compound also makes it an interesting candidate for X-ray photoelectron spectroscopy (XPS) and the Mössbauer spectra study in the pure LiFePO4 and carbon containing LiFePO4/C ceramics. The LiFePO4 powders for the XPS and Mössbauer spectra study have been synthesized by solid state reaction and LiFePO4/C composites were synthesized by a sol-gel method and later sintered in argon gas.The ceramics of LiFePO4 was sintered in air. The binding energies of Fe 2p, P 2p and O 1s core level of the LiFePO4 ceramics and LiFePO4/C composite surfaces have been determined by XPS at room temperature. The analysis of Fe 2p, P 2p and O 1s core level XPS deconvolution is presented in this work. Mössbauer spectroscopy in the temperature range from 10 K to 700 K has been applied in order to determine phase transition temperatures, the Debye-Waller factor and typical ionization states of iron in compounds. Behavior of Li+ ions was evaluated in the second coordination sphere of iron based on changes in hyperfine parameters of Mössbauer spectra.