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The thermal stability of several isotactic polypropylenes and propylene-co-1-nonene copolymers is assessed under nitrogen by means of thermogravimetric analysis (TGA). The samples involve wide ranges of molecular weight, isotactic average length, and 1-nonene content, in order to perform a comprehensive analysis of the effect that chain features exert on the apparent activation energy (Ea), in the initial stages of the molten state degradation. The degradation process correlates with chain mobility and, accordingly, with chain features that are linked to. Thus, microstructure and chain size are found to play a key role. In fact, isotactic average length of propylene sequences and molecular weight are driving factors in the Ea required for main chain thermal scission.