The development of LiFePO<sub>4</sub> as a cathode materials on lithium-ion battery was increased with the use of additional techniques such as atomic doping and coating. The material used in this report was LiFeSi<sub>0.06</sub>P<sub>0.94</sub>O<sub>4</sub>/C (LFP Si-6%), synthesized with doping silicon 6% and 11wt% carbon coating by a solid state method. X-ray Absorption Spectroscopy (XAS) characterization was used to investigate the effect on electronic and atomic structure of LFP Si-6%, especially in X-ray Absorption Near Edge Strucuture (XANES) region. XANES data measured on Fe K-edge and Si K-edge. Fe foil, FeO, Fe<sub>2</sub>O<sub>3</sub>, FePO<sub>4</sub>, Si powder, SiO, SiO<sub>2</sub> were used as a standard sample for comparison with the result of LFP Si-6%. XANES analysis showed that the energy absorption of Fe K-edge and Si K-edge in LFP Si-6% was 7124.94 eV and 1846.16 eV, respectively. The oxidation state of Fe was Fe<sup>2.576+</sup> between Fe<sup>2+</sup> and Fe<sup>3+</sup>, while Si was close to the estimation of Si<sup>4+</sup>. In addition, the linear combination fitting (LCF) in XANES Fe K-edge was performed to show the ratio of Fe<sup>2+</sup>/Fe<sup>3+</sup> (FeO/Fe<sub>2</sub>O<sub>3</sub>).