From previous investigations of the alkaline dehydrochlorination of PVC it is well known that polyene sequences are formed. In this paper the true overall kinetics of the dehydrochlorination reaction between PVC and alcoholic KOH in tetrahydrofuran solution was studied at 9.5°C by measuring the rate of disappearance of KOH. Titrations of the hydroxide ions consumed and the chloride ions evolved showed close agreement. IR spectra of the samples did not show any evidence of substitution by hydroxide ions. Small amounts of DMSO present in the solvent were found to increase the reaction rate markedly. The kinetic scheme was discussed and the first rate constant was determined. Preliminary results of reactions of the polyene sequences with various reagents are presented. These reactions were made in order to introduce new functional groups into the PVC chains.