The electrodeposition of carbon films with a Mo2C interlayer was investigated in LiCl-NaCl-Na2CO3 melts at 900 degrees C. Cyclic voltammetry was applied to study the electrochemical reaction mechanism on Mo and Pt electrodes, indicating that, two reduction reactions including carbon deposition and carbon monoxide evolution, may take place on the two electrodes simultaneously during the cathodic sweep. Carbon films with a continuous Mo2C interlayer were prepared by constant voltage electrolysis, showing a good adhesion between Mo substrate and carbon films. The carbon films with a Mo2C interlayer were characterized using X-ray diffraction measurement, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy. The results reveal that carbon materials deposited on the electrodes are mainly composed of graphite and carbon diffusion in Mo (or Mo2C) leads to the formation and growth of Mo2C interlayer. (C) 2015 Elsevier BAT. All rights reserved.