An asymmetric bis(1,3-benzoxazine) monomer based on deoxybenzoin has been synthesized through Mannich condensation. The chemical structure of this deoxybenzoin-based monomer has been confirmed using H-1 NMR, C-13 NMR, FT-IR and elemental analysis. The assignments for the oxazine protons and carbon atoms in the asymmetric structure have also been confirmed using two-dimensional (2D) NMR techniques, including H-1-H-1 nuclear Overhauser effect spectroscopy (NOESY) and H-1-C-13 heteronuclear multiple quantum coherence spectroscopy (HMQC). In addition, the effect of incorporation of deoxybenzoin on the mode of polymerization of benzoxazine has been investigated using differential scanning calorimetry (DSC), in situ FT-IR and H-1 NMR spectroscopy. This deoxybenzoin containing bis(benzoxazine) exhibits a low polymerization temperature resulting from a unique self-catalyzed cationic polymerization mechanism. Furthermore, the thermal stability of the resulting polybenzoxazine has been studied using thermogravimetric analysis (TGA). This deoxybenzoin-based polybenzoxazine exhibits high thermal stability and low flammability, with a T-d5 temperature of 403 degrees C, a high char yield value (68%) and low total heat release (THR of 11.4 kJ/g).