Influence of temperature on the anti-corrosive properties of a diamond-like carbon (DLC) coating, produced using plasma-enhanced chemical vapor deposition (PECVD) on the S355 steel substrate (S355/DLC), was investigated. Corrosion test of the materials were carried out using the electrochemical method. The corrosive environment was an alkaline solution of sodium chloride. The heat treatment of the materials was carried out in air atmosphere, at 400 and 800 °C. It was demonstrated that the DLC coating effectively protected the S355 steel surface from coming into contact with an aggressive corrosive environment. It was found, based on a corrosion test after a heat treatment at 400 °C, that the anti-corrosive properties of the DLC coating did not undergo significant changes. Due to the changes in the surface structure of S355/DLC, the microhardness (HV) of the DLC layer increased. However, after a heat treatment at 800 °C, the carbon coating on the S355 steel surface was destroyed and, thus, lost its protective effect on the substrate.