The application of alkoxyamines as initiators/controllers in nitroxide mediated polymerization and as agents for theranostics requires the development of switchable (from stable one to labile one) alkoxyamines. One way to achieve this is to tune the polarity of various groups carried by either the alkyl fragment or the nitroxyl fragment. Thus, the effect of protonation/deprotonation of the para-functionalized aryl moiety carried by the alkyl fragment in diethyl(2,2-dimethyl-1-((1,1-dimethylethyl)(1-para-subsitutedphenylethoxy)amino)propyl)phosphonate is investigated. An increase in kd is observed with increasing localized electrical effect, i.e., in the presence of electron withdrawing groups at the para position of the phenyl ring. A striking effect of the intimate ion pair on kd is also observed.