The C-ON bond homolysis in alkoxyamine 2a was chemically triggered by quaternization of the 1-(pyridin-2-yl)ethyl fragment using protonation, acylation, and oxidation into the N-oxide. The solvent effect was also investigated, and DFT calculations were performed to explore this chemical activation. Alkoxyamines 2a-d were also compared to the 1-(pyridin-4-yl)ethyl analogues 3a-d.