Bulk and surface chemical states were both investigated for electrochemically delithiated LixFePO4 using {7}Li and {31}P MAS NMR spectroscopy. The quantitative lithium extraction/insertion from LiFePO4 and the reversible two-phase reaction behavior between LiFePO4 and FePO4 were confirmed on electrochemical operation. The {7}Li and {31}P NMR spectra of the fully charged LixFePO4 evidenced a single Li-poor phase Li0.05FePO4 instead of a biphasic mixture of 0.05LiFePO4 and 0.95FePO4. Simultaneous growth of LixPOyFz was also shown as a surface film component on the charged electrodes, which dynamically increased and decreased in intensity during charging and discharging reactions, respectively. The electrode surface was further characterized with XPS to discuss the surface film formation during electrochemical cycles. Combined chemical state analyzes by NMR and XPS spectroscopies suggested that the degradation of LiPF6 salt occurred from the initial redox cycles, but that of solvent occurred after multiple cycling. The deposition of carbonaceous species would be related to a small capacity fading observed after the multiple charge-discharge cycles.