The catalytic performance of Ni/SBA-15 catalysts promoted with different loadings of Pd is investigated for the thermocatalytic decomposition of methane into COx-free hydrogen and nanocarbon. The catalysts are characterized in terms of their structural, textural and redox properties. The results showed that the Pd deposition increased the crystallinity of NiO and allowed the fine dispersion of NiO on the SBA-15 support. The decreased surface area of SBA-15 after Ni loading, due to pore blocking, increased after the Pd deposition. Moreover, it reduced the reduction temperatures of NiO interacting with the SBA-15 due to the spillover effect of hydrogen. Furthermore, the addition of Pd increased the catalytic efficiency of the catalysts. A maximum hydrogen yield of 59% is observed over the 0.4% Pd catalyst within 30 min of time on stream. No deactivation is observed until 420 min of streaming for all of the catalysts, indicating a high catalytic stability of the Ni/SBA-15 catalysts for methane decomposition. A new set of multi-walled carbon nanotubes with open tips were deposited over the catalysts, irrespective of the role of Pd and its loading. Moreover, a high graphitization degree and oxidation stability are observed for the nanotubes deposited over the 0.4% Pd catalyst. (C) 2015 Elsevier B.V. All rights reserved.