Methane decomposition offers an interesting route for the CO(2)-free hydrogen production. The use of carbon catalysts, in addition to lowering the reaction temperature, presents a number of advantages, such as low cost, possibility of operating under autocatalytic conditions and feasibility of using the produced carbons in non-energy applications. In this work, a novel class of carbonaceous materials, having an ordered mesoporous structure (CMK-3 and CMK-5), has been checked as catalysts for methane decomposition, the results obtained being compared to those corresponding to a carbon black sample (CB-bp) and two activated carbons, presenting micro- (AC-mic) and mesoporosity (AC-mes), respectively. Ordered mesoporous carbons, and especially CMK-5, possess a remarkable activity and stability for the hydrogen production through that reaction. Under both temperature programmed and isothermal experiments, CMK-5 has shown to be a superior catalyst for methane decomposition than the AC-mic and CB-bp materials. Likewise, the catalytic activity of CMK-5 is superior to that of AC-mes in spite of the presence of mesoporosity and a high surface area in the latter. The remarkable stability of the CMK-5 catalyst is demonstrated by the high amount of carbon deposits that can be formed on this sample. This result has been assigned to the growth of the carbon deposits from methane decomposition towards the outer part of the catalyst particles, avoiding the blockage of the uniform mesopores present in CMK-5. Thus, up to 25 g of carbon deposits have been formed per gram of CMK-5, while the latter still retains a significant catalytic activity. (C) 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.