The electronic structure of LiC6 has been investigated by soft X-ray absorption and emission spectroscopies. The results reveal that upon full lithiation of graphite, the Li 2s electrons are transferred into the carbon π* states in a near rigid-band behavior, resulting in the increased density of states near EF and the shift of σ* states to lower energies. In addition, the resonant inelastic X-ray scattering spectra of LiC6 do not show strong dispersive features as that of graphite, indicating that the crystal momentum is not conserved during the scattering process due to the delocalization of electrons in the intermediate state.