Thermal analysis of polystyrene, poly(p-methylstyrene) and poly(α-methylstyrene) has been carried out using evolved-gas analysis by infrared and mass spectrometry, and direct-pyrolysis analysis by mass spectrometric techniques. Evolved-gas analysis, both by infrared and mass spectrometry, reveals features due mainly to the corresponding monomers or stable, volatile, and low relative molecular mass degradation products. In direct-pyrolysis mass spectrometry, however, primary decomposition products and heavier fragments such as dimers and trimers can also be detected. The ion-temperature profiles of the corresponding monomer ions reveal information about the thermal stability of the polymers.