Kinetic investigation of the reaction of electrochemically generated$$0_2 ^{\mathop - \limits_ \bullet } $$with perfluorooctene, styrene, and cyclohexene in acetonitrile, in the presence of tetraethylammonium perchlorate used as a background electrolyte, revealed that$$0_2 ^{\mathop - \limits_ \bullet } $$reacts with styrene and perfluorooctene at the double bond, and the reactivity of the olefins with respect to$$0_2 ^{\mathop - \limits_ \bullet } $$decreases with decrease in the electrophilicity of the substituents at the double bond: perfluorooctene>styrene>cyclohexene. The main transformation products of styrene are phthalic and benzoic acid esters.