The interfacial impedance between PVDF/HFP-based electrolytes and lithium metal continues to increase and attains a delicate kinetic equilibrium upon prolonged storage. The graphite anode, on the other hand, is found to remain inert towards the electrolytes. Its interfacial impedance does not vary with increasing storage time or in the presence of different lithium salts. In addition, it is found that the impedance of a Li–C half-cell consists of the impedances of two interfaces and is therefore often mistakenly used in the interpretation of the behaviour of a single carbon electrode. Thus, a three-electrode impedance study is required. It is found that an inductive loop appears in the low-frequency region of the impedance spectrum of a carbon electrode immediately after the first lithium-intercalation step, which probably implies that an adsorption–desorption phenomenon might exist at the interface. Moreover, another inductive effect, which arises from the connecting leads, also appears in the high-frequency region. Finally, the cathode is found to be the major source of cell impedance and increases with increasing cycle number.