The pyrolysis kinetics of low-density polyethylene, high-density polyethylene, polypropylene, and polystyrene has been studied at temperatures below 450 °C. In addition, a literature review on the low-temperature pyrolysis of these polymers has been conducted and has revealed that the scatter in the reported kinetic data is significant, which is most probably due to the use of simple first-order kinetic models to interpret the experimental data. This model type is only applicable in a small conversion range, but was used by many authors over a much wider conversion range. In this investigation the pyrolysis kinetics of the forementioned polymers and a mixture of polymers has been studied at temperatures below 450 °C by performing isothermal thermogravimetric analysis (TGA) experiments. The TGA experimental data was used to determine the kinetic parameters on the basis of a simple first-order model for high conversions (70-90%) and a model developed in the present study, termed the random chain dissociation (RCD) model, for the entire conversion range. The influence of important parameters, such as molecular weight, extent of branching and ß-scission on the pyrolysis kinetics was studied with the RCD model. This model was also used to calculate the primary product spectrum of the pyrolysis process. The effect of the extent of branching and the initial molecular weight on the pyrolysis process was also studied experimentally. The effect of the extent of branching was found to be quite significant, but the effect of the initial molecular weight was minor. These results were found to agree quite well with the predictions obtained from the RCD model. Finally, the behavior of mixtures of the aforementioned polymers was studied and it was found that the pyrolysis kinetics of the polymers in the mixture remains unaltered in comparison with the pyrolysis kinetics of the pure polymers.