The research presented details chemical modifications of poly(vinyl chloride) (PVC) and its derivative, dehydrochlorinated PVC (DH-PVC) through the use of two grafting techniques, namely a normal fullerenation, using AIBN (2,2-Azoisobutyronitrile), and the atom transfer radical addition (ATRA). The products were characterized and the presence of new FTIR peaks at 528 and 577 cm(-1) along with new H-1-NMR signal at 3.9 ppm, suggested that fullerenes has been grafted to the polymer molecules. Percentage of C-60 in the fullerene grated products determined by UV/Visible spectroscopy initially increased with the amount of fullerene used to a maximum value (approximate to 5.66 % wt) before decreasing again. It was also determined that the C-60 content of the fullerene grafted PVC product prepared by using ATRA, was notably greater than that obtained using the normal fullerenation approach, regardless of the amount of C-60 used. When the dehydrochlorinated PVC was used as the starting polymer for fullerenation, the fullerene grafted DH-PVC using ATRA, was markedly insoluble in many common solvents (THF and dichlorobenzene). This was not the cases for the fullerene grafted DHPVC prepared via an AIBN based fullerenation. Furthermore, the electrical conductivity values of the modified PVC products determined by using a four-point probe method were found to increase linearly with the amount of C-60 present. Overall our data suggest that the suitable and efficient techniques for grafting C-60 onto PVC and DHPVC chains are ATRA and AIBN-based fullerenation, respectively. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2410-2421, 2013