A series of mesoporous Ni/TiO2 catalysts with different loadings of nickel from 10 to 50 wt% was successfully prepared via a facile one-pot sol-gel route; characterized for its structural, textural and redox properties; and tested for the non-oxidative thermocatalytic decomposition of undiluted methane for the first time. The characterization results reveal the presence of both NiO and NiTiO3 and metallic nickel as active metal phase in the fresh and reduced catalysts, respectively. Spherical catalyst particles were found to be highly inter-aggregated and to provide a porous texture to the catalyst. All of the prepared catalysts exhibited high catalytic activity and stability for methane decomposition. It is due to the fine dispersion of active nickel nanoparticles on the surface of the TiO2 support with proper metal-support interaction. Moreover, with increasing nickel loading and reaction temperature, the yields of hydrogen and nanocarbon were found to be significantly increased. A maximum hydrogen yield of 56% and a final carbon yield of 1544% were obtained for the 50% Ni/TiO2 catalyst at 700 degrees C with an undiluted methane feed of 150 ml/min for 360 min of time on stream. The catalyst showed high catalyst stability, for a period of 960 min of time on stream and similar to 24% hydrogen yield was observed at the end of long-term run using the 50% Ni/TiO2 catalyst. Moreover, irrespective of the nickel loading involved, bulk amount of multiwalled carbon nanotubes were deposited on the surface of the catalyst. XRD and Raman analyses of the spent catalysts showed that the crystallinity of nanocarbon increased with increasing nickel loadings, whereas the graphitization degree remained unaffected, with an I-D/I-G value of 0.88. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.