Fe-Co/Al2O3 catalysts were developed and tested in the catalytic decomposition of methane (CDM) for the synthesis of multi-wall carbon nanotubes (MWCNT) and the CO2-free hydrogen production. While Fe (54.5-66.7 mol.%) is the main active phase for the carbon formation on the catalyst, Co acts as dopant aiming to improve its overall catalytic behaviour. Catalysts with Co contents of up to 18.2 M% showed the presence of alpha-Fe and Fe-Co crystallites with different size and lattice parameter. Fe1-xCox alloy with bcc crystal system was identified only for Co contents of 14.0% and above, and presented a lattice constant lower than alpha-Fe, which would modify the carbon diffusion of the metal particle during the MWCNT growth. Co inhibited the Fe3C formation during CDM resulting in higher carbon formations and longer activity times. This phase, shown in undoped catalysts, favored the presence of bamboo-type carbon nanotubes. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.