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Ion‐endohedral‐fullerene has attracted growing interest due to the unique electronic and structural characteristics arising from its distinctive ionic nature. Although there has been only one reported ion‐encapsulated fullerene, Li+@C60, a significant number of fundamental and applied studies have been conducted, making a substantial impact not only in chemistry and physics but also across various interdisciplinary research fields. Nevertheless, studies on ion‐endohedral fullerenes are still in their infancy due to the limitations in variety, and hence, it remains an open question how the size and symmetry of fullerene, as well as the motion and position of the encapsulated ion, affect their physical/chemical properties. Herein, we report the synthesis of lithium‐ion‐endohedral [70]fullerene (Li+@C70 X−, X=PF6− and TFSI−), a novel ionic endohedral fullerene. X‐ray crystallography confirmed the encapsulation of Li+ by C70 cage as well as its ion‐pair structure stabilized by external TFSI− counter anion. The encapsulated Li+ drastically lowered the orbital energy of the C70 cage by Coulomb interactions but did not affect the orbital energy gap and degeneracy. DFT studies were also performed, which supported the experimentally observed electronic effects caused by the encapsulated Li+. [ABSTRACT FROM AUTHOR]