Rate constants k(d) of the C-ON bond homolysis in a new type of alkoxyamines (initiator/controller for Nitroxide Mediated Polymerization) carrying alkyl fragments capable of protonation were measured. A 20-fold increase was reported for the protonated alkoxyamine compared to the non-protonated homologue as predicted (Chem. Soc. Rev., 2011).