Abstract: Internally plasticized PVC copolymers were prepared by grafting PVC with butyl acrylate and 2-(2-ethoxyethoxy)ethyl acrylate by atom-transfer radical polymerization, resulting in well-behaved polymers with a wide range of glass transition temperatures (–54 °C to 54 °C). When the grafted side chains made up more than 50% of the polymer by weight, the glass transition temperatures were below 0 °C. The covalent attachment of the plasticizing grafts requires one simple procedure starting from commercial PVC, making this strategy an industrially relevant and environmentally friendly alternative to the use of conventional small-molecule plasticizers.