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It is topical now to find the ways of hydrogen production that would eliminate emission of carbon oxides into the atmosphere and provide implementation of the so-called low-carbon economy. The production of hydrogen via thermocatalytic methane decomposition (CMD) on carbon catalysts makes it possible to obtain not only a valuable environmentally friendly fuel represented by hydrogen but also various carbon materials that could be applied in different industries. The use of carbon catalysts is essential for economic efficiency of the methane decomposition process. This work is a review of CMD fundamentals and a brief report on the catalytic activity of carbon materials (activated carbon, carbon black, nanotubes and nanofibers) differing in their structure, physical and chemical properties, which were studied in the indicated process. The main problems and prospects for application of this technology were revealed.