X-ray absorption spectroscopy and X-ray tomography has been used as powerful techniques for probing the electrode microstructure and the atomic structure of electrode materials. Metal L-edge XAS results show that Ni ions at the surface are oxidized to Ni during charge, whereas Ni ions in the bulk are further oxidized to Ni during charge. The P K-edge XAS was studied to investigate the electronic structure of the delithiated Li FePO material, and it shows that the electrochemical delithiation of LiFePO results in the hybridization of P 3p states with the Fe 3d states. Recent advances in tomographic techniques have enabled three dimensional microstructural characterization of a wide range of materials with unprecedented resolution. Focused ion beams (FIBs) have also been successfully been employed in the study of lithium ion battery microstructures.