Introduction of bis(fluorosulfonyl)imide (FSI) as an anion to an ambient-temperature ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium (EMI) as well as lithium (Li) cations can provide a reversible Li intercalation into a graphitized electrode, while such intercalation is completely irreversible without FSI. The surface-layer components on the graphitized electrodes, cycled in the ionic liquid electrolytes with and without FSI, were found to be chemically similar based on X-ray photoelectron spectroscopy. Ac impedance spectroscopy revealed that the resistance of the electrode charged with FSI was much lower even than that charged in a solvent electrolyte system containing ethylene carbonate (EC) and dimethyl carbonate (DMC). On the basis of these physicochemical analyses, the origins of cycleability in the presence of FSI are discussed.