Solar catalytic decomposition of methane (SCDM) was investigated in a solar furnace facility with different catalysts. The aim of this exploratory study was to investigate the potential of the catalytic methane decomposition approach providing the reaction heat via solar energy at different experimental conditions. All experiments conducted pointed out to the simultaneous production of a gas phase composed only by hydrogen and un-reacted methane with a solid product deposited into the catalyst particles varying upon the catalysts used: nanostructured carbons either in form of carbon nanofibers (CNF) or multi-walled carbon nanotubes (MWCNT) were obtained with the metallic catalyst whereas amorphous carbon was produced using a carbonaceous catalyst. The use of catalysts in the solar assisted methane decomposition present some advantages as compared to the high temperature non-catalytic solar methane decomposition route, mainly derived from the use of lower temperatures (600-950 degrees C): SCDM yields higher reaction rates, provides an enhancement in process efficiency, avoids the formation of other hydrocarbons (100% selectivity to H-2) and increases the quality of the carbonaceous product obtained, when compared to the non-catalytic route. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.