The effect of molybdate on the passivation of AISI 1020 carbon steel under open-circuit conditions in pH 12.5 calcium hydroxide solutions containing chloride was investigated via electrochemical tests and surface characterization techniques. In the early stage, molybdate increased the rate of passivation, with inhibition efficiency being positive. During the later stage, after the carbon steel has passivated, precipitation of calcium molybdate over parts of the sample surface resulted in slight negative inhibition efficiency and the passive film was found to have a higher proportion of ferrous cations and a smaller thickness. However, the precipitation of a thick calcium molybdate film over the entire surface can reverse this situation, increasing the polarization resistance through a cathodic inhibition mechanism. The electrochemical and XPS results showed that regardless of its effect on the final polarization resistance, the presence of calcium molybdate precipitates led to a decrease in the total extent of carbon steel oxidation, indicating an overall beneficial effect. Molybdate was also shown to be effective against localized corrosion, with 14.6 mM molybdate sufficient in preventing passivity breakdown in pH 12.5 solution containing 564 mM chloride. (C) The Author(s) 2016. Published by ECS. All rights reserved.