The charging (lithiation) and discharging (delithiation) of a Ni–Sn alloy electrode was examined by means of holographic interferometry and laser scanning confocal microscopy (LSCM). The developing concentration profile of Li+ ion during discharging (delithiation) of the Ni–Sn alloy electrode agreed reasonably well with the prediction based on transient diffusion theory, indicating that the cell configuration successfully suppressed natural convection due to the electrochemical reaction. The morphological variation of Ni–Sn alloy electrode during charge/discharge cycle could be observed very clearly by in situ LSCM. It was found that the contraction of active material during the discharge (delithiation) initiates cracks in the Ni–Sn alloy electrode.