New methane degradation nickel catalysts based on original and modified layered double hydroxides and multilayer carbon nanotubes have been synthesized. The synthesized systems have been characterized by a set of physicochemical methods, namely, X-ray diffraction (XRD) analysis, scanning electron microscopy, Raman spectroscopy, and the thermal method. The catalytic activity of the synthesized catalysts in the temperature range of 550–850°С has been studied. It has been shown that in the methane decomposition reaction, the sample with a modified Ni-containing layer exhibits two regions of catalytic activity (550–650 and 700–850°С), whereas the sample based on carbon nanotubes is characterized by a single region (700–850°С) and the system based on a layered double hydroxide does not show activity in the entire temperature range.