Catalytic pyrolysis has been used to upgrading the quality of pyrolytic liquids. Herein, we report a comprehensive study on the catalytic pyrolysis of waste tires using Ni/SiO2 as catalysts. The analyses were carried out by combining thermogravimetry (TGA), TGA interfaced to a Fourier Transform Infrared spectrometer (TGA–FTIR), and pyrolysis coupled to gas chromatography/mass spectrometer (Py–GC/MS) techniques. During waste tire decomposition, the main functional groups detected in the FTIR were alkenes, aromatics, and heteroatoms-containing groups such as nitrogen, sulfur, and oxygen. Meanwhile, by Py-GC/MS were identified mainly D,L-limonene, isoprene, benzene, toluene, xylenes (BTX), and p-cymene. The Py–GC/MS experiments at three different temperatures (350, 400, and 450 °C) suggested an effect of the catalyst on product distribution. The Ni catalyst promoted cyclization reactions and subsequently aromatization, leading to an improved vapors composition. The use of iso-conversional kinetic models along with master plots allows proposing a multiple-step reaction mechanism, which was well described by the Avrami-Erofeev, Random Scission, and truncated Sestak–Berggren models. The values of activation energies show differences for the catalyzed and uncatalyzed pyrolysis (111.0 kJ mol-1 and 168.4 kJ mol-1), validating the effectivity of Ni/SiO2. Finally, the thermal Biot (>1) and PyI and PyII numbers (10-3<PyI <10-1 and 10-2< PyII<10-3) confirms that the process is being occurred between the kinetic and the convection-limited regimes.