Abstract—Effect of the structural mechanical modification via the crazing mechanism and composition of films based on HDPE nanocomposites and highly dispersed silica particles on the thermo-oxidative degradation and pyrolysis is studied. The incorporation of highly dispersed silica particles into the polymer matrix causes a reduction in the onset temperature of the intense weight loss of the composites by about 30°С and an increase in the temperature interval by 100°С under conditions of thermo-oxidative degradation. It is shown that in pyrolytic decomposition the HDPE‒SiO2 composite also starts to lose weight at lower temperatures (smaller by 50°С). Using various kinetic approaches to process the TGA curves the activation energy for each stage of thermal oxidation and pyrolysis is determined for structurally different HDPE-based samples. In the case of thermo-oxidative degradation, dependence of the activation energy on conversion is shown to be complex, thereby reflecting the multistage nature of the process. In pyrolysis, the activation energy is almost constant at all stages of the process. For various models of the processes, the activation energy is calculated by the Coats–Redfern method and the most probable mechanisms of thermal degradation and pyrolysis of the samples are proposed.