The covalent attachment of [60]fullerene (C-60) to two poly(vinyl chloride) (PVC) samples with different isotactic content is achieved by direct reaction in o-dichlorobenzene (o-DCB) solution in the presence of AIBN. The extent of fullerenation is controlled by varying the C-60 feed ratio. The pendant C-60-chemically modified PVC polymers are soluble in tetrahydrofuran (THF) and have been characterized by UV-vis, NMR, FTIR, DISC, TGA, cyclic voltammetry, and SEM. The quantitative microstructural analysis after covalent attachment of the bulky C-60 moiety to the PVC has been followed by C-13 NMR spectroscopy. From the results it can be concluded that the modification of PVC by graft reaction through free radical reaction proceeds by a stereoselective mechanism. This conclusion has been confirmed on the basis of the increase of the glass-transition temperature (T-g) and the thermal stability of the C-60-chemical modified PVC samples. The fullerenated PVCs obtained show good electron acceptor properties, as evidenced by electrochemical investigations. (c) 2007 Wiley Periodicals, Inc.