Targeted synthesis of C/composite Ni-based material was carried out by the method of matrix isolation. The composite was formed with regard to the features of the reaction of catalytic decomposition of methane. The morphology and physicochemical properties of these materials have been characterized using a number of methods: elemental analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, temperature programmed reduction (TPR-H2), specific surface areas (SSA), thermogravimetric analysis, and differential scanning calorimetry (TGA/DSC). It was shown by FTIR spectroscopy that nickel ions are immobilized on the polymer molecule of polyvinyl alcohol, and during heat treatment, polycondensation sites are formed on the surface of the polymer molecule. By the method of Raman spectroscopy, it was shown that already at a temperature of 250 °C, a developed conjugation system with sp2-hybridized carbon atoms begins to form. The SSA method shows that the formation of the composite material resulted in a matrix with a developed specific surface area of 20 to 214 m2/g. The XRD method shows that nanoparticles are essentially characterized by Ni, NiO reflexes. The composite material was established by microscopy methods to be a layered structure with uniformly distributed nickel-containing particles 5–10 nm in size. The XPS method determined that metallic nickel was present on the surface of the material. A high specific activity was found in the process of catalytic decomposition of methane—from 0.9 to 1.4 gH2/gcat/h, XCH4, from 33 to 45% at a reaction temperature of 750 °C without the stage of catalyst preliminary activation. During the reaction, the formation of multi-walled carbon nanotubes occurs.