Electrochemical studies of the reduction and oxidation reactions of five different organic nitroxyls have been performed across a wide pH range (0-13). The resulting Pourbaix diagrams illustrate structural effects on their various redox potentials and on the p Ka values of the corresponding hydroxylamine and hydroxylammonium ions. Evidence is also given for the reversible formation of a hydroxylamine N-oxide when nitroxyls are oxidized in alkaline media. Structural effects on the thermodynamics of this reaction are assessed.