AbstractThe chlorination of poly(vinyl chloride) (PVC) was investigated by using deuterated polymeric models of PVC, viz., α‐deuterated PVC (α‐d‐PVC) and β,β‐dideuterated PVC (β,β‐d2‐PVC). The chlorinated samples of PVC, α‐d‐PVC, and β,β‐d2‐PVC were examined by combining infrared (IR),1H‐NMR,13C‐NMR, and mass spectroscopy. The results obtained were used in a study of the reaction mechanism of PVC chlorination. The selectivity of chlorination and the extent of the substitution and elimination‐addition mechanism of chlorination are discussed with respect to the degree of chlori