Benzoxazines are a kind of high-performance thermosetting resin that can undergo ring-opening polymerization to generate cross-linking structures. Here, two benzoxazine monomers, bisphenol A/aniline type (BA-a) and bisphenol A/tert-butylamine type (BA-tb), were synthesized and mixed with three tertiary amine catalysts like 2-methylimidazole (2MI), 1,2-dimethylimidazole (12MI), 4-dimethylaminopyridine (DMAP). Differential scanning calorimetry (DSC) was performed to study the curing behaviors and the curing kinetics of two benzoxazine/catalyst systems. The results indicated that all amines had a catalytic effect on the polymerization of both benzoxazines, and the BA-a/catalyst systems showed relatively higher activity. In addition, Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectra were procured to analyze structural changes in the benzoxazine/catalyst systems during the curing process. The presence of the catalysts promoted the progress of the ring-opening reactions and the formation of the phenolic units in the cross-linking structures, and these evolutions were more obvious for the BA-a/catalyst system than the BA-tb/catalyst system. Furthermore, a thermogravimetric analysis (TGA) was conducted to analyze the thermal stability of the cured systems. Finally, possible curing reaction mechanisms were proposed for these benzoxazine/amine systems.