During the electrolysis of molten KH-2HF, a solid CF film is formed on carbon anodes. The influence of the potential applied to the anode on the composition of the CF surface film was studied by XPS and NMR. Results obtained with carbon electrochemically passivated in molten KF-2HF have been compared with those obtained with carbon simply immersed in molten KF-2HF without any polarization. Whatever the potential, and even in the case of carbon sample immersed in molten KF-2HF without any polarization, the presence of covalent and semi-ionic C–F bonds has been pointed out both by XPS and NMR. For polarized samples, the higher the potential applied to the anode in KF-2HF, the higher the fluorination level. From investigations carried out with carbon activated at 40V in molten KF-2HF, it was concluded that the electropolishing of the surface induced by this treatment allows enhancing drastically the fluorine evolution reaction.