An environmental-friendly volatile corrosion inhibitor for carbon steel comprises sodium silicate with the mass-volume concentration of 0.8 g / L-1.2 g / L, alanine with the mass-volume concentration of 1.8 g / L-2.3 g / L, sodium benzoate with the mass-volume concentration of 6.8 g / L-8.3 g / L, and ammonium benzoate with the mass-volume concentration of 3.8 g / L-4.5 g / L, dissolved in distilled water. A preparation method of the environmental-friendly volatile corrosion inhibitor comprises the following steps: respectively weighing the sodium silicate, alanine, sodium benzoate and ammonium benzoate according to the mass-volume concentrations; respectively dissolving in distilled water with the volumes of 1 / 4 of those of the solutes, and uniformly stirring; after the four solutions are stilled, mixing and uniformly stirring. The environmental-friendly volatile corrosion inhibitor is formed by compounding the sodium silicate, alanine, sodium benzoate and ammonium benzoate, is environmental-friendly and efficient, has little pollution to the environment, has a good synergistic effect, and solves the problems that the conventional volatile corrosion inhibitor is poor in corrosion-inhibition performance and generates more pollution, adopts the simple preparation method, is convenient to use, and can prolong the service life of the carbon steel.