Metallofullerenes of the group IV element Hf have been synthesized in a macroscopic quantity for the first time. The species were purified by HPLC and identified to be Hf 2 C 8 0 and HfC 8 4 by TOF/MS measurement. Their HPLC behavior toward the Buckyprep and 5PBB columns were studied systematically in comparison with those of other known fullerene species and HfC 8 4 is found to have an abnormally large capacity factor for the former column. The UV/VIS/NIR spectrum observed for Hf 2 C 8 0 and found to include absorption peaks at 406, 511, 567 and 668 nm. No ESR signal could be observed for Hf 2 C 8 0 .