Anthraccne-photosensitized cationic polymerization of cyclohexene oxide at lambda=350 nm in conjuction with onium salts, namely N-ethoxy-2-methyl pyridinium hexafluorophosphate (EMP+PF6-) or diphenyliodonium hexafluorophosphate (Ph(2)l(+)PF(6)(-)), in the presence of a stable radical, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), yielded polymers with alkoxyamine terminal groups, These polymers were found to be efficient initiators for stable free radical polymerization (SFRP) of styrene. LR, H-1-NMR spectral analysis and GPC studies of the obtained polymers show that block copolymers are readily formed as a result of combination of photosensitized cationic and stable free radical polymerization mechanisms.