To understand the complex hydrogen bonding structure, several phenolic derivatives and benzoxazine model compounds are synthesized and characterized by Fourier transform infrared spectroscopy (FT-IR). The estimation of molar extinction coefficients for various types of hydrogen bonding species is systematically carried out by the curve-resolving of FT-IR spectra. The distribution of hydrogen bonding species in benzoxazine model dimers is quantitatively analyzed. It is revealed that benzoxazine dimers and BA-a polybenzoxazine are mainly composed of intramolecular interaction rather than intermolecular interaction.