Highly labile SG1-based alkoxyamines were synthesized using the photodecomposition of both azo compounds and dithiocarbamates. The former method was a straightforward procedure to obtain the alkoxyamines, but a high [azo]/[nitroxide] ratio is needed. The latter method required only a stoichiometric amount of dithiocarbamate and allowed the recovery of the disulfide after irradiation. This enabled combination of the two methods in a process where only 0.75 equiv of azo compound is needed and where sulfurous compounds acted only as intermediates.