One isomer of C 60 (i-C 3 F 7 ) 8 , three isomers of C 60 (i-C 3 F 7 ) 6 , and the first mixed perfluoroalkylated fullerene, C 60 (CF 3 ) 2 (i-C 3 F 7 ) 2 , have been isolated by HPLC from a mixture prepared by reaction of C 60 with heptafluoroisopropyl iodide in a glass ampoule at 260–290°C. The molecular structures of the four new compounds have been determined by means of X-ray single crystal diffraction partially also by use of synchrotron radiation. Theoretical calculations at the DFT level of theory have been employed to rationalize the energetics of isomers and of C 60 -R f binding.