Both flexible and rigid forms of poly(vinyl chloride) (PVC) were effectively dechlorinated in NaOH/ethylene glycol (EG) solution during ball mill pulverization. The high degree of dechlorination obtained was attributed to the increased surface area of the crushed PVC particles and the resulting enhancement of contact between the PVC and dissolved hydroxide ions. The common additives diisononyl phthalate and CaCO3 were easily separated from the PVC bulk during the dechlorination reaction. The reaction proceeded under chemical control, with degrees of dechlorination for both flexible and rigid PVC increasing with temperature with apparent activation energies of 110 and 80 kJ/mol, respectively. This reaction was accurately represented by a modified shrinking-core model.