The electrochemical behavior of a graphite anode in 2.4NaF/AlF3-0.05wt% Al2O3 molten salt was investigated via cyclic voltammetry (CV) and chrono-electrochemical techniques. Four oxidation current peaks, located at 1.42, 2.5, 3.1, and 3.94 V vs. Al/Al3+, were observed in CV curves, which may be attributed to the formation of CO2, CF4, graphite fluoride ((CF)(n)), and F-2, respectively. The anode effect occurred when the potential exceeded 3.5 V. Meanwhile, the mechanism of the electrode reaction of CO2 and (CF)(n) formation was confirmed to be irreversible charge transfer followed by a chemical reaction. Therefore, we confirmed that the passivation of the graphite anode was due to the formation of (CF)(n) on the electrode surface, blocking the mass transfer. According to the number of the charge transfer and the characteristics of the electrode reactions, we discuss detailed reaction pathways for CF4 and (CF)(n) formation. In addition, the presence of the small quantity of C2F6 in the anode gas is discussed. (C) 2014 The Electrochemical Society. All rights reserved.