For the first time, natural graphite is successfully fluorinated electrochemically using triethylamine tri(hydrofluoride) (C(2)H(5))(3)N center dot 3HF adduct. The nature of the C-F bond formed in graphite fluoride is deduced from FT-IR, Raman and XPS spectroscopy. Electrochemical discharge of the semi-ionic fluorinated graphite as cathode in magnesium cell is investigated and the discharge capacity of the C-F electrode is found to be 548 mAh/g. Graphite-fluorine cathode prepared by this procedure showed rechargeable nature in combination with magnesium anode. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3610991] All rights reserved.