Catalytic decomposition of methane is an environmentally attractive approach to CO2-free hydrogen production. The decomposition of methane over carbon nanofibers was carried out in a fixed bed flow reactor. The objectives of this study are to demonstrate the activity of carbon nanofibers for methane decomposition in comparison with that of carbon black and to investigate the nature of active sites in the carbon catalysts. The catalytic activities of different carbon catalysts were found in the following order: carbon nanofiber > HI-900L carbon black > N330 carbon black > non-catalyst. After investigating the surface area and mass of the carbon catalysts after methane decomposition, the nature of active sites was discussed.