Ce@C-82 is isolated by high-performance liquid chromatography (HPLC) and the cage symmetry is determined as C-2v by measuring the C-13 NMR spectra of its anion. The C-13 NMR peaks of [Ce@C-82](-) show temperature-dependent shifts ascribed to the f electron remaining on the Ce atom. Both Ce@C82 and [Ce@C-82](-) are silent in electron spin resonance spectroscopy (ESR) because of the highly anisotropic g matrix as well as of the fast relaxation process originating from the orbital angular momentum of the f electron. This is the complementary relationship to the observation of the paramagnetic shift in 13 C NMR. [Ce@C-82](-) has lower stability in air than [La@C-82](-).