Direct coal liquefaction residue was used as the precursor for preparing hierarchical micro-/macro-mesoporous carbon by KOH activation with addition of Al2O3, and the resultant carbon AlRC was used as the catalyst for catalytic methane decomposition. The results indicate that the carbon AlRC shows excellent methane conversion, up to 61% after 10 h. Besides hydrogen production from methane decomposition, fibrous carbons were formed on the AlRC catalyst, which is different from other carbon catalysts. The investigations of the formation and growth of the fibrous carbon on the carbon catalyst and its catalytic performance indicated that the formed fibrous carbon contribute to the high methane conversion of AlRC catalyst. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.