The photopolymerization ability of photosensitized alkoxyamines has been investigated. These compounds behave as interesting two-component photoinitiators. Laser flash photolysis, electron spin resonance, and density functional theory allow to support the interactions encountered between the photosensitizer (benzophenone and isopropylthioxanthone) and the alkoxyamines (C-O bond breaking and hydrogen transfer) and the side reactions of the nitroxide radical with photosensitizer (electron transfer). (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2910-2915, 2010