Graphite basal surface is inert, and decomposition of n-alkanes on the graphite surface has not been discovered. We here report the evidence of decomposition of n-octanes on highly oriented pyrolytic graphite (HOPG) surface, heat-treated up to 1200 °C under high vacuum (10(-7) Pa), at near room temperatures. Using a temperature programmed desorption apparatus equipped with a quadrupole mass spectrometer showed the production of hydrogen molecules, methane, and ethane, suggesting that the protonation of n-octane takes place on graphite surface at near room temperature. It is known that acidic functional groups are terminated at edges on the air-cleaved HOPG surface and they increase their acidity via reactions with water. However, it is most unlikely that they protonate n-alkanes at near room temperature such as superacids. We anticipate that superacidic protons, which can protonate n-octanes, are produced on the graphite surface through a novel reaction mechanism.