The surface of lithium has been analyzed in a dry-air atmosphere and in 1 M LiClO 4 /PC by in situ AFM observation and FTIR spectroscopy. High-resolution AFM discloses the nano-structure of the lithium surface which consists of grain boundaries, many ridge-lines, and flat areas. After immersing lithium in LiClO 4 /PC, these lines swelled and large particles appeared. The surface chemistry of lithium has been examined by ex situ XPS and SAM. It is found that Li 2 CO 3 and Li 2 O localize on the ridge-lines and the grain boundaries. The morphological change due to lithium deposition occurs as a formation of particles on the ridge-lines and the grain boundaries.