Fullerenes decorated with poly(vinylidene fluoride) (PVDF) were synthesized in a three-step procedure: Iodine transfer polymerization of vinylidene fluoride with C6F12I2 as the chain transfer agent was carried out in supercritical carbon dioxide to synthesize iodine-terminated PVDF, which was subsequently transformed to azide-terminated polymer. Finally, azide-terminated PVDF chains were attached to a fullerene core under microwave irradiation at 160 degrees C in 1.5 h. The materials were characterized by NMR, FT-IR, UV/vis, GPC, elemental analysis, and DSC. On average, 4-5 PVDF chains are attached to one C-60 moiety. FT-IR spectra and DSC measurements indicate that the polymer end groups strongly affect the crystallinity of the material. For PVDF with azide end groups and PVDF attached to fullerenes the fraction of the beta polymorph is dominant while alpha polymorphs are almost absent.