In this study, a set of three new silica-based embedded with NiO and/or MgO nanocatalysts (SBNs) have been prepared and tested for the pyrolysis of scrap tires (STs). The intent is to identify and optimize the best nanocatalyst that decreases the operating temperature and speeds up the pyrolysis reaction rate. The influence of the three prepared SBNs nanocatalysts on STs was scrutinized using thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR). The kinetic triplets were estimated utilizing the isoconversional method of the Ozawa–Flynn–Wall (OFW) corrected model. Experimental TGA and FT-IR results showed a thermal decomposition of all volatile organic additives alongside the polyvinyl compounds at a lower temperature in the presence of these SBNs. However, a competitive decomposition behavior appeared for each SBN nanocatalysts. The kinetic triplets’ findings showed different effective activation energy trends at two different conversion regions (low and high conversions), suggesting different reaction mechanisms confirmed by the reaction kinetic models. Interestingly, NiO-MgO-SBNs showed the highest reaction rate for this thermo-pyrolysis of STs, which could be because of synergetic interaction between NiO and MgO nanoparticles. Moreover, the results of the change in Gibbs free energy of activation (ΔG‡) indicated the promising catalytic activity for those SBNs by promoting the spontaneity of pyrolysis reaction. These proof-of-concept findings could promote the futuristic use of NiO-MgO-SBNs at the industrial level toward sustainable ST pyrolysis.