The regularities and mechanism of the electrochemical borating of cathodic carbographite materials under the conditions of electrolysis of cryolite–alumina melts are studied. The effect of carbon surface wetting is proved to take place upon the formation of a melted aluminum layer at a cathode. These facts are confirmed by X-ray diffraction analysis of the surface layer of the cathode. Compounds TiC and TiB2 are observed. The mechanisms of electrochemical and physical processes of the formation of Ti–B–C complexes in the surface layers of the cathode are studied.