PVC was subjected to a chemical modification aiming at replacing the chlorine atoms by pyridine groups via a homolytic route. Pyridine groups were peculiarly affixed to the PVC matrix via a carbon-carbon bond rather than a carbon-nitrogen one. PVC was first iodinated using the Conant-Finkelstein reaction, followed by the application of the homolytic conditions of Minisci to generate pyridinated PVC with a varying degree of substitution. The extent of substitution was not high; the reaction on 30% iodinated PVC afforded a degree of modification no greater than 3%. PVC was subjected to a chemical modification aiming at replacing the chlorine atoms by pyridine groups via a homolytic route. Pyridine groups were peculiarly affixed to the PVC matrix via a carbon-carbon bond rather than a carbon-nitrogen one. PVC was first iodinated using the Conant-Finkelstein reaction, followed by the application of the homolytic conditions of Minisci to generate pyridinated PVC with a varying degree of substitution. The extent of substitution was not high; the reaction on 30% iodinated PVC afforded a degree of modification no greater than 3 %.