The thermal degradation of a series of polybenzoxazines based on bisphenol A and various aliphatic amines has been studied. Using the hyphenated techniques of thermogravimetric analysis-Fourier transform infrared spectroscopy (TGA-FTIR), and gas chromatography-mass spectrometry (GC-MS), the mechanisms of thermal decomposition have been proposed. It is also proposed that the Mannich base in polybenzoxazines plays a significant role in the thermal degradation of polybenzoxazines. The contribution of hydrogen bonding to the degradation mechanism of the Mannich base has been examined. The proposed mechanisms have also been supported through the thermal degradation study of benzoxazine model dimers.