In this study, we investigated the relationship between the thermal stability and physicochemical microstructure of EV (ethylene-vinyl chloride) copolymer prepared by reductive dechlorination of PVC with tributyltin hydride. The EV copolymer grades varied in both molecular weight and ethylene content, the latter being in the range of 21-61 mol% ethylene. The thermal stability of EV copolymer was studied by thermogravimetic analysis (TGA). It was found that the rate of dehydrochlorination decreased with increase in degree of alternation of comonomer units in the copolymer and the homogeneity of its physical morphology. This study appears to substantiate the explanation put forward by Braun et al. and Naqvi for the thermal stability of this copolymer.