Using intermittent X-ray diffraction, an understanding of the time dependence of phase evolution in the electrode materials during lithium extraction can be determined. Phase evolution in both coated and uncoated nano-scale LiFePO4 samples upon chemical delithiation has been investigated by this technique. Different kinetic behaviors are observed in the two samples and the technique helps to understand the delithiation mechanism in the nano-scale LiFePO4 and is able to resolve phase evolution in seconds’ resolution.