For steels of different grades, the effect of the chemical composition, structure, and surface etching on the contact potential difference is studied using the Kelvin probe method. It was shown experimentally that, with a change in the structure and chemical composition, the contact potential difference changes. Etching the surface of the steel with a 4% solution of nitric acid leads to a sharp decrease in the magnitude of the contact potential difference, which allows us to conclude that the value of the electron work function from the sample surface increases. The ability to control the composition and structure of the material by the Kelvin probe method is shown.