Three kinds of novel aromatic diamine-based benzoxazines containing naphthalene, propane-2,2-diyldibenzene and neopentyl groups in the backbone, respectively (designated as BAPNCP, BAPBACP and BAPNPGCP, respectively), were synthesized and characterized. In addition, the effects of backbone structures on curing behaviors of the monomers and thermal and flammability properties of the resulting polymers were systematically studied. The results indicated that BAPNPGCP displayed the highest enthalpy of the curing reaction associated with the ring-opening of benzoxazine, which was due to the effect of benzoxazine ring content per unit mass. Interestingly, the 5 wt% weight loss temperature and char residue after thermogravimetric test for poly(BAPNPGCP) were 8 ℃ and 7% higher than those of poly(BAPBACP). Meanwhile, the total heat release of poly(BAPNPGCP) was less than half of that for poly(BAPBACP), indicating the substantial effect of benzoxazine ring content on flammability and char formation. Furthermore, it was found that poly(BAPNCP) gave the best thermal stability and flame retardancy, which was due to the synergistic effect between naphthalene group and benzoxazine ring content. This study provides new insight into the curing behavior of benzoxazine and further understanding on the high performance of polybenzoxazine.