Mn(salen)Cl was applied as a low-cost catalyst for the formation of alkoxyamines from nitroxides and substituted styrenes. These "unimolecular initiators" for nitroxide-mediated radical polymerization (NMRP) were synthesized using 2,2,6,6-tetramethyl-1-piperadine -1-oxyl and 2,2,5-trimethyl-4-phenyl-3-azahexane-3-azahexane -3-oxyl. Functionalized alkoxyamines were obtained from 4-vinylbenzyl chloride and 4-vinylbenzyl alcohol. The divinyl compound 1,2-bis(4-vinylphenyl)ethane was converted to an alkoxyamine monomer and to bisaminooxy compounds, which can be used as "biradical initiators" for NMRP.