The use of a bisaminooxy compound as initiator for nitroxide-mediated radical polymerization (NMRP) of styrene or n-butyl acrylate allows the synthesis of alpha,omega-nitroxide-capped polymers. At high temperatures and with the addition of acetic anhydride, it was found that these polymers could be applied as macroinitiators in the free-radical polymerization of methyl methacrylate. This enables the synthesis of block copolymers with only minor contents of homopolymer.