In this work, five catalysts (three zeolites and two ordered mesoporous aluminosilicates, MCM-41) were tested for the pyrolysis of two samples of commercial ethylene-vinyl acetate (EVA) copolymers with different vinyl acetate percentage and different melt flow index. This study was carried out by using a thermobalance under nitrogen atmosphere and with a heating rate of 10°C min−1. As can be expected, the preliminary analysis of TG curves shows differences depending on the chemical and structural characteristics of the polymer and of the catalyst used: (i) despite that the temperature of maximum decomposition rate is always the same for the first decomposition step (acetic acid loss), the presence of catalyst makes this step less selective, thus occurring within a wider range of temperatures, especially for those catalysts with high external surface areas; (ii) the catalysts produce a reduction of the temperature of the second decomposition step (cracking of the residue from the first step) which is always lower than that of the thermal process; (iii) it seems that the greater decrease of the maximum decomposition rate temperature occurs when Hβ zeolite is added and is followed by the addition of Al-MCM-41 (however, the effect of the addition of catalyst depends on its percentage); and (iv) the comparison of TG curves corresponding to the addition of Hβ and Al-MCM-41 (which have high external surface areas), and of HY and H-ZSM-5 (with much lower external surface areas) reveals the importance of the accessibility to the active sites in the behavior of the catalyst.