Abstract: The TiB2 as inert cathode material for aluminum electrolysis, was electrodeposited successfully on carbon cathode as a coating by way of molten salts electrolysis at 800°C for 3 hours with a current density 0.3 A/cm², of which the composition of the electrolyte used is 4.8KC1-55.7KF-15.3 K2TiF6-24.2 KBF4 in % as mass fraction. XRD was used to detect the composition of the coating with the Electron Probe Micro Analyzer (EPM) used for morphology observation. The results showed that the coating is composed of a single compound, i.e., TiB2 without inclusions. The 0.2 mm-thick TiB2 coating is smooth and appears metallic luster, especially it is bonded firmly to the carbon substrate. It is confirmed that Ti and B can be co-deposited to form a TiB2 coating on carbon surface as an inert cathode in this way.