The pH-dependent kinetics of C-ON bond homolysis reactions of the four alkoxyamines (viz., the derivatives of 2-(4-(dimethylamino)-2-ethyl-5,5-dimethyl-2-(pyridin-4-yl)-2,5-dihydro-1H-imidazol-1-oxyl and 2-(2-carboxyethyl)-5,5-diethyl-2,4-dimethyl-2,5-dihydro-1H-imidazol-1-oxyl) in water solution have been scrutinized using DFT calculations (M06-2X/6-311++G(2df,p) level of theory with the PCM model). On the basis of computations, the experimental results obtained before (J. Org. Chem. 2011, 76, 5558) have been rationalized. The concentration dependence of all possible protonated forms of the four alkoxyamines was obtained from pH measurements. The contributions of particular protonated forms into the overall rate constants of thermolysis were estimated using the DFT calculated Gibbs free energies Δ(r)⁰G of C-ON bond homolysis reactions. The computations revealed that the observed rate constants of thermolysis of the two species at several pH values are dominated by decomposition reactions of two or even three protonated forms. The observed trends in reactivity of the alkoxyamines were mainly attributed to destabilization of the radical products of C-ON bond scission reactions. A linear correlation between the sum of radical stabilization energies (RSEs) of products of thermolysis and the calculated Gibbs free energies of reactions was found for various protonated forms of the species studied. Apart from this, the linear correlation exists between the relative RSE and nitrogen hyperfine constants aN of various protonated forms of the nitroxide radical products.