Blackening belongs to the predominant technological processes in preserving steel surfaces from corrosion by generating a protective magnetite overlayer. In place of the commonly used dipping-procedure into nitrite-containing blackening baths at boiling temperatures that are far above 100 °C, here we describe a more environmentally friendly electrochemical route that operates at temperatures, even below 100 °C. After an investigation of the electrochemical behavior of steel samples in alkaline solutions at various temperatures, the customarily required bath temperature of more than 130 °C could be significantly lowered to about 80 °C by applying a DC voltage that leads to an electrode potential of 0.5−0.6 V vs. Pt. Thus, it was possible to eliminate the use of hazardous sodium nitrite economically and in an optimum way. Electrochemical quantification of the corrosion behavior of steel surfaces that were in contact with 0.1 M KCl solution was carried out by linear sweep voltammetry and by Tafel slope analysis. When comparing these data, even the corrosion rates of conventional blackened surfaces are of the same magnitude as a blank steel surface. This proves that magnetite overlayers represent rather poor protective layers in the absence of additional sealing. Moreover, cyclic voltammetry (CV), atomic force microscopy (AFM), scanning electron microscopy (SEM) and auger electron spectroscopy (AES) characterized the electrochemically blackened steel surfaces.