The ammonia-hydrazine shutdown protection method is widely used in thermal power plants in China because of its good protective performance. However, the toxicity and safety of hydrazine have restricted its use in many power plants, and it is necessary to improve the shutdown protection techniques. In this paper, electrochemical impedance spectroscopy and potentiodynamic polarization curves were used to study the effect of hydrazine in water solutions of different pH values, adjusted with ammonia on the corrosion behavior of carbon steel. It was found that in the water solution without hydrazine, the corrosion resistance of a carbon steel electrode increased with raising the pH. When the pH value of water increased to 10.5, the impedance value of the carbon steel increased significantly, the corrosion current density decreased from 26.06 μA·cm −2 at pH 10.0 to 2.36 μA·cm −2 , and the steel surface was passivated. Hydrazine had different effects on the electrochemical corrosion behavior of carbon steel in water solutions with various pH. When the pH of water was not higher than 10.0, hydrazine had a good corrosion inhibition effect on carbon steel. When the pH of water was not lower than 10.5, the addition of hydrazine inhibited the passivation of carbon steel and promoted the corrosion. The adsorption and substitutional oxidation of hydrazine in the anode region of carbon steel surface should be the reasons for the above phenomenon.