Charge density analysis by single-crystal X-ray diffraction using high-energy synchrotron radiation reveals molecular structure of C
60 fullerene containing lithium atom, Li@C
60. Weak charge density peaks of the lithium atom are clearly reconstructed near the centers of six-membered rings of the C
60 cage. The molecular structure of Li@C
60 is quite different from that of C
60 fullerene containing a gas molecule at the cage center such as H
2@C
60. The existence of electrostatic attractive interaction between a Li
+ cation and SbCl
6− anions through the C
60 cage is suggested from the crystal structure.
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