Novel Ni and Co supported on aluminosilicate hollow sphere catalysts were investigated to decompose methane into CO and CO2 free hydrogen and carbon nanotube. The hollow sphere structure was prepared by reverse microemulsion method and then Ni and Co were loaded by the impregnation method. The fresh catalysts and deposited carbon were characterized by several microscopic and spectroscopic techniques. The catalytic results showed that the Co based catalyst exhibited higher activity and durability at longer reaction time, due to the higher number and distribution of metal sites. The hollow sphere structure of the support could protect the metal particles against aggregation during the catalytic reactions. Accordingly, higher metal dispersion, stabilization and catalytic performance were achieved. The formation of nickel silicate is the main reason for the lower decomposition activity of Ni based catalyst at longer reaction time. TEM and Raman spectroscopic data revealed that the Co-based catalyst produced a relatively uniform diameter of MWCNTs with higher crystallinity and graphitization degree compared to the Ni-based catalyst. (C) 2013 Elsevier B.V. All rights reserved.