Vinyl chloride (VC) as well as other vinyl monomers interact with oxygen of the air to give peroxide compounds. It is known that the course of this reaction has some influence on the production process of polyvinyl chloride (PVC) as well as on the properties of the polymer. The whole problem of VC autoxidation in connection with the polymerization of this monomer was discussed in the sixties in Russian [l]. No new review of the publications concerning autoxidation of VC is available. In a recent interesting review [2] devoted to the formation and degradation of polymeric peroxides, only a small part of the literature about peroxides based on VC was mentioned, and important aspects of the VC autoxidation problem were not touched upon. In this review, an attempt is undertaken to represent comprehensive information about the reaction of VC with oxygen, chemical structure and reactions of the oxidation products, the role of small amounts of oxygen in VC polymerization, and the dependence of PVC properties on the presence of oxygen in the polymerization mixture. Pathways for the prevention of the negative effect of oxygen during polymerization are also discussed. In this review, we do not enter into the field of VC polymerization initiated by systems containing oxygen and reducers such as trialkylbor and other metallorganic compounds. The role of oxygen in the destruction processes occurring after the polymer has been formed is also not discussed.