Activators regenerated by electron transfer–atom radical transfer polymerization (ATRP) as a controlled living polymerization are distinguished by their acceptance of small amounts of transition-metal complexes and oxygen and by their tolerance of reducing agents at a high concentration. The precondition of all ATRP applications is the use of homolytic or heterolytic cleavable halides as a dormant species; this allows the propagation of monomer chains. Hence, alkyl bromides are slightly cleavable and are the preferred initiators for ATRP. The bromination of polymer slides used as macroinitiators was carried out under gentle bromoform plasma conditions. This led to an oxidation-resistant stable bromine layer. More than 20 bromines per 100 carbons on the polymer scaffold were permanently bound to the substrate after plasma treatment. The resulting amounts of secondary and tertiary bromines on the polymer scaffold exhibited a suitable macroinitiator concentration for the surface-initiated polymerization of methyl methacrylate and glycidyl methacrylate. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40662.