A new alkoxyamine based on a highly thermally stable nitroxide is used for the controlled polymerization of styrene and butyl acrylate at temperatures up to 200 °C. High monomer conversions are reached in a few minutes with a linear increase in polymer chain-length with conversion, a final dispersity (Đ) of ∼1.2, and successful chain-extension of the resulting material. The alkoxyamine concentration was altered to target various chain lengths, with autopolymerization dictating the polymerization rate of styrene regardless of alkoxyamine concentration. Controlled polymerization of methacrylate monomers and acrylic acid was successful with the addition of styrene. The new material opens the possibility to increase the range of specialty products made for applications in coatings, inks, overprint varnishes, and adhesives.