We studied the changes in the electronic structure of LiFePO4 induced by Ti-, Al-, and Cu-doping. The technique used in the study was Fe 2p and O 1s X-ray absorption (XAS) spectroscopy. XAS spectra were analyzed using atomic multiplet and band structure calculations. Fe 2p XAS spectra show that the Fe ions in LiFePO4 are in a divalent Fe2+ high-spin state, and that the Fe ions remain in this Fe2+ state in the Ti-, Al-, and Cu- doped materials. O 1s XAS spectra present relatively weak transitions to mixed O 2p-Fe 3d states at threshold (the transitions to O 2p-Fe 3sp states appears at higher energies due to the larger hybridization). O 1s XAS spectra of the doped materials show additional absorption intensity just below threshold. These features correspond to transitions to doped states in the bandgap of the LiFePO4 compound. © 2005 The Electrochemical Society.