Detailed structural studies of two lithiated metal oxides, Li2CuO2 and nanoscale LiCoO2, have been carried out using ex situ high-energy X-ray diffraction (XRD) and in situ X-ray absorption spectroscopy (XAS) with the objective of understanding structural changes that might cause capacity loss during cycling. XRD on the cuprate was studied at various states of charge and phase composition, and the bulk state was determined by Rietveld refinement and pair density function (PDF) analysis. Results showed a largely irreversible structural change of the material upon oxidation of Cu2+ as well as CuO formation. The in-situ XAS of the LiCoO2 was analyzed through a difference method to extract the changes in the local structure that occur upon cycling in both the near edge (XANES) and extended region (EXAFS). Results suggest that cycling causes site exchange of the Co and Li ions near the surface of the nanoscale LiCoO2.