A new method for observing the outermost surface morphology and the thickness of solid electrolyte interphase (SEI) are presented. Low acceleration voltage in extreme high resolution scanning electron microscopy (XHR-SEM) provides detailed information on the SEI surface morphology due to secondary electron contrast mechanism. Also, XHR-SEM under low acceleration voltage with low energy induced ion etching in x-ray photoelectron spectroscopy (XPS) studies provides valuable information on the SEI layer thickness. More detailed properties of the SEI layer were investigated by transmission electron microscopy (TEM).