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For Li‐ion and Na‐ion batteries, the intercalation behavior of graphite anodes is quite different. While Li‐ions intercalate, Na‐ions only co‐intercalate with solvent molecules from the electrolyte solution leading to ternary graphite intercalation compound (t‐GIC) formation along with an expansion of the graphite interlayer spacing to 1.2 nm. This large interlayer spacing represents a micropore with parallel slit geometry. Little is known about t‐GIC formation, but it is commonly believed that throughout the reaction the ion is accompanied by either a full or partial solvation shell. Here, it is elucidated for the first time, using two independent methods – mass measurements and electrochemical impedance spectroscopy – supplemented by operando microscopy, entropymetry and simulations, that the storage mechanism is far more complex. A new model for the electrochemical solvent co‐intercalation process is proposed: As soon as solvated ions enter, the graphite structure is flooded with free solvents, which are subsequently replaced by solvated ions. Close to full sodiation, few free solvents remain and structural rearrangement take place to reach the full storage capacity. Thus, t‐GICs represent a unique case of switchable microporous systems and hence appear as a bridge between ion storage in the bulk phase and in micropores, i.e., between batteries and supercapacitors. [ABSTRACT FROM AUTHOR]