Ampoule reactions of C 70 with n- and i-C 3 F 7 I were carried out at 250–310°C. Two step HPLC separations allowed the isolation of several C 70 (n-C 3 F 7 ) 4–8 and C 70 (i-C 3 F 7 ) 4 compounds. Crystal and molecular structures of C 70 (n-C 3 F 7 ) 8 -V, C 70 (n-C 3 F 7 ) 6 O, C 70 (n-C 3 F 7 ) 4 , and three isomers of C 70 (i-C 3 F 7 ) 4 have been determined by X-ray crystallography using synchrotron radiation. Molecular structures of the new compounds were compared with the known examples and discussed in terms of addition patterns and relative energies of their formation.