The covalent attachment of [60] fullerene (C-60) to isotactic polypropylene (i-PP) is achieved by direct reaction in 1,2,4-trichlorobenzene (TCB) solution in the presence of dicumyl peroxide (DCP). The chemically modified pendant C-60/i-PP Polymers are soluble in chlorinated solvents and have been characterized by ultraviolet-visible and fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, differential scanning calorimetry, cyclic voltametry, and thermogravimetric analysis. From the results it can be concluded that the modification of i-PP by grafting via a free-radical reaction competes with the possibility of chain scission of i-PP due to the presence of DCP. The functionalized polymers crystallize in the monoclinic crystal modification, and have high crystallinity. The incorporation Of C60 significantly enhances the thermal stability of the i-PP Electrochemical measurements demonstrate good electron acceptor properties of the fullerenated i-PP samples. (c) 2008 Wiley Periodicals, Inc.