In this study, electrolytic oxidation reactions of alkylphosphites such as triethylphosphite (TEP), diethylphosphite (DEP), trimethylphosphite (TMP) and dimethylphosphite (DMP) were elucidated with cyclic voltammetry in acetonitrile solvent using Pt, graphite, tin, copper and lead electrodes and 0.1 M NaClO4 supporting electrolyte. The voltammograms showed that Pt electrode was the most suitable an ode material. Other electrodes did not give satisfactory results. The voltammograms obtained were evaluated according to Nicholson-Shain criteria and it was concluded that the oxidation was of ECE type and completely irreversible. Oxidative addition of these electroactive compounds with organic substrates such as benzene and toluene were also been investigated.