Pyrolysis is gaining more significance as a technology used to produce alternative fuels and chemicals. This study dealt with the catalytic pyrolysis of a realistic waste mixture of multi-layered plastic food packaging. The thermal behavior, kinetic parameters, and kinetic model of multi-layered plastic food packaging pyrolysis were determined to show its potential for process scale-up. In particular, we aimed to evaluate the effect of a ZSM-5 zeolite catalyst, modified with iron(III) oxide. The pyrolysis process on this decagonal structure was investigated using thermogravimetric analysis under nitrogen flow at four heating rates ranging between 40 and 600 °C. The kinetic study was conducted using the model-free isoconversional Friedman method as well as advanced statistical analysis to determine the reaction mechanism of the process. The thermal decomposition occurred in the range of 350–510 °C, with a mass loss greater than 90%. The kinetic study revealed a complex pyrolysis process, which consisted of three decomposition stages, diffusion, and Avrami-Erofeev reaction types. The activation energy values determined by the Friedman method rose with the degree of conversion, from 127 kJ mol⁻¹ at 0.01 to 219 kJ mol⁻¹ at 0.95. The doping of the catalyst lowered the activation energy of the reaction by 44% and 8% in the first and second stages, respectively, and increased the acidity of the zeolites, thus enhancing the reactivity on the surface of the catalysts. Lower activation energy meant less energy was required to heat the pyrolysis reactor since the onset temperature of sample decomposition was reduced.