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This paper deals with the main concepts of the modern theory of poly(vinyl chloride) (PVC) degradation, which embrace the key problems concerning the chemical structure and the content of anomalous groups in PVC, their influence on the thermal stability of polymer products, the kinetics of HCL elimination. In contrast to the universally recognized ∼‐chloroallyl activation of the process of PVC degradation, a conception of the prime role of oxygen‐containing chloroallyl groups of type ∼C(O)CHCHCHCl∼ (CAG) has been developed. It has been shown that PVC real macromolecules contain approximately 10−4 mole/PVC mole oxygen‐containing ∼C(O)CHCHCHCl∼ groups determining PVC low thermal stability. It has been found that the monomer purity, the presence of oxygen in the reaction area, the temperature of vinyl chloride polymerization, etc., considerably affect CAG content in PVC macromolecules.