(CeC82)-C-@ has been isolated with a purity of similar to 99.5% by an efficient solvent extraction procedure, followed by HPLC separation. The UV-vis-near-IR absorption spectrum of the metallofullerene was measured at a wavelength range from 300 to 2100 nm, X-ray photoelectron spectroscopy (XPS) of (CeC82)-C-@ has been studied. The results suggest that, analogous to the La in (LaC82)-C-@, the Ce in (CeC82)-C-@ donates three valence electrons to the carbon cage as opposed to two electrons suggested by a recent ab initio calculation.