Electrochemical intercalation of potassium into graphite in molten potassium fluoride at 1163K was investigated by means of cyclic voltammetry, galvanostatic electrolysis and open-circuit potential measurements. It was found that potassium intercalated into graphite solely between graphite layers. In addition, the intercalation compound formed in graphite bulk in molten KF was quite unstable and decomposed very fast. X-ray diffraction measurements indicate that a very dilute potassium–graphite intercalation compound was formed in graphite matrix in the fluoride melt. Analysis with scanning electron microscope and transmission electron microscope shows that graphite was exfoliated to sheets and tubes due to lattice expansion caused by intercalation of potassium in molten KF.