Some basic properties and compatibility toward lithium electrode for electrolytes based on substituted imidazolium ionic liquid have been investigated. The ionic liquids having imidazolium cation substituted by methylcarboxyl or cyano group suffers from low conductivity. However, reversible lithium deposition–dissolution process was observed in electrolytes based on these electrolytes. In particular, lithium salt solution in cyanomethyl-substituted imidazolium ionic liquid provided similar cycle efficiency to conventional organic solvent electrolyte at constant-current condition. The mixed ionic liquid electrolyte containing the cyanomethyl-substituted ionic liquid also provided good cycle performance despite of containing large amount of 1-ethyl-3-methyl imidazolium (EMI)-based ionic liquid. Such mixed electrolyte system serves both the stability of lithium electrode process and valid conductivity for practical use.