O-substituted hydroxylamines which are known to initiate and promote nitroxide-mediated radical polymerization were synthesized in high yield by a novel and facile synthetic approach. Using the favorable Mn(OAc)(3) as electron transfer agent in the in situ generation of benzylic radicals and their trapping by nitroxide radicals provides a new powerful and more economic way to the desired alkoxyamine initiators for this controlled, living radical polymerization. TEMPO, TIPNO and the protected tris-hydroxy derivative of TIPNO were used to synthesize the appropriate alkoxyamines.