The electrochemistry of steel in aerobic and anaerobic aqueous alkaline solutions was studied with or without forced convection to investigate the cathodic processes occurring on steel exposed by defects in polymer coated steel pipe. The results are relevant to the mechanistic understanding of the effect of cathodic protection on the disbonding of fusion bonded epoxy (FBE) coatings on steel. Moderate (pH 9.8) and strongly (pH 14) alkaline aqueous solutions were used to simulate the water layers at the cathodically polarized steel surface on the soil-side of buried pipe. A rotating gold ring and steel disc electrode (RRDE) in alkaline aqueous electrolyte equilibrated with 1 atm oxygen over solution was used to measure the rotation rate dependent current for the electroreduction of oxygen, O-2, On an ASTM A516 steel disc and the resulting peroxide generation, which was determined by monitoring the oxidation current on the gold ring. An appreciable fraction of the oxygen reduction current on the steel disk gave rise to peroxide generation over a wide range of potentials, from -0.2 to -0.9 V vs SCE in 1 M KOH. The observation of peroxide generation is noteworthy, because oxidizing agents, such as peroxide and its decomposition products, superoxide and hydroxy radical, can degrade the polymers used for coating pipelines. As result, oxidative degradation of polymer or interfacial compounds may be a cause of the accelerated disbonding observed for protective coatings on steel pipelines under cathodic protection.