We proposed the nitrone-oxaziridine rearrangement as a novel method for photochemical activation for the homolysis of alkoxyamine in nitroxide-mediated polymerization. The photoisomerization of the aldo-/ketonitrone-group into the oxaziridine one in 2,5-dihydroimidazole 3-oxide-based alkoxyamines was studied; the products of photolysis have been identified, and quantum yields were measured. Conversion of the nitrone group into the oxaziridine one was found to decrease the activation energy of alkoxyamine homolysis by ca. 10 kJ mol-1.