Abstract Analyses of Li has been performed by reflection electron energy-loss spectroscopy (REELS) technique, using a scanning electron microscopy (SEM) apparatus, where Li signals can be detected with high spatial resolution without severe requirements for sample shapes. For Li 4 Ti 5 O 12 and Li 7 Ti 5 O 12 samples as electrode materials of Li-ion batteries, the Li distribution was successfully revealed by the spectrum-imaging scheme. The fine structure of REELS spectra was able to be applied to the chemical analysis of Li-containing compounds.