Charge transfer kinetics at the Li metal electrode/electrolyte interface for three inorganic solid electrolytes and an organic liquid electrolyte were elucidated with two parameters, exchange current density (i 0 ) for Li/Li + couple reactions and ionic conductivity in electrolyte. The former was evaluated by potential step method with a microelectrode, while the latter was done by electrochemical impedance spectroscopy. Both i 0 and ionic conductivity showed Arrhenius type dependence, and activation energies (E a ) for the charge transfer reactions and ionic conduction were evaluated. In the case of the organic liquid electrolyte, E a for the Li/Li + couple reactions was higher than that for ionic conduction because of the solvation/desolvation of Li + ion. However, for the Li 2 S-P 2 S 5 solid solid electrolytes, the E a for the Li/Li + couple reactions was quite close to that for ionic conduction due to the lack of the solvation/desolvation.