The electrochemical properties of various iron oxide scales on steel exposed in saturated calcium hydroxide solutions were investigated. The iron oxide scales were manufactured by different heat treatments and grinding processes and characterized using X-ray diffraction and scanning electron microscope. The electrochemical properties of the scales were assessed by measuring the corrosion potential and using electrochemical impedance spectroscopy and potentiodynamic polarization curves. It was found that wustite and magnetite are less noble compared to hematite but are more effective as cathodic surfaces. The results show that the electrochemical properties of the mill scale can be an important contributing factor in the corrosion of steel in concrete.