We focused on the Li+ transfer at an interface between solid and liquid electrolytes by using asymmetric electrochemical impedance measurements to clarify the solvation and desolvation processes of Li+ ions. When DC voltage was imposed on the interface, the current-direction dependency of interfacial Li+-transfer resistances was observed. Consequently, we would conclude that the desolvation process of Li+ transfer from liquid to solid electrolytes mainly governed the interfacial Li+ transfer.