New experimental results on perfluoroalkylation of C 60 and C 70 with the use of R f I (R f =CF 3 , C 2 F 5 , n-C 3 F 7 , n-C 4 F 9 , and n-C 6 F 13 ), along with a critical overview of the existing synthetic methods, are presented. For the selected new fullerene (R f ) n compounds we report spectroscopic, electrochemical and structural data, including improved crystallographic data for the isomers of C 70 (C 2 F 5 ) 10 and C 60 (C 2 F 5 ) 10 , and the first X-ray structural data for the dodecasubstituted perfluoethylated C 70 fullerene, C 70 (C 2 F 5 ) 12 , which possesses unprecedented addition pattern.