The catalytic performance of copper promoted nickel/alumina catalysts was studied in thermocatalytic dissociation of methane for production of COX-free hydrogen and carbon nanofibers. Copper addition to nickel catalysts improved the catalytic performance due to increase in methane adsorption, higher reducibility and nickel dispersion on the catalyst surface. In addition, high affinity of copper with graphite structure prevents the generation of encapsulation carbon on the nickel surface and hinders the catalyst deactivation. The catalytic results confirmed that the increase in reaction temperature enhanced the CH4 conversion. However the excessive increase in reaction temperature decreased the reactant (CH4) conversion and catalyst lifetime. (C) 2017 Elsevier Ltd. All rights reserved.