The electrochemical behavior of enamel coated carbon steel in simulated concrete pore water solution with various chloride concentrations was investigated by open circuit potential, linear polarization resistance, and electrochemical impedance spectroscopy tests. The phase composition, microstructure, and tensile strength of enamels were characterized by X-ray diffraction, scanning electron microscopy, and pull-off tests. Three types of coatings with pure, mixed, and double enamels were studied and compared for their corrosion behavior. Test results indicated that all three types of enamel coatings can reduce the corrosion current density of carbon steel in an alkaline environment with chloride; the pure and double coatings are superior to the mixed enamel coating. Cohesive failures were observed within the three coatings while their interface with the steel substrate remained intact. In comparison with the pure enamel, the mixed enamel was stronger with smaller open channels formed due to the addition of calcium silicate and the double enamel was weaker with larger air bubbles trapped in the inner pure enamel layer by the outer mixed enamel layer.