In order to solve the problems of brittleness and high curing temperature of polybenzoxazines, first, benzoxazine hydrochloride was synthesized with Bisphenol A-based Benzoxazine (BZ) monomer and hydrochloric acid. Second, Bz-MMT was prepared via ion-exchange reaction between Na-montmorillonite (Na-MMT) and benzoxazine hydrochloride, and then was characterized by FTIR, XRD and TGA. Thirdly, curing behavior of the mixture of BZ monomer and Na-MMT, or the mixture of BZ monomer and Bz-MMT, was followed by DSC. Fourthly, polybenzoxazine/montmorillonite nanocomposites PBZ/Na-MMT and PBZ/Bz-MMT were prepared by heating these mixtures of BZ monomer and MMT. Finally, TGA was used to test the thermal stability of PBZ and PBZ/Bz-MMT nanocomposites. The results show that for Bz-MMT, the basal spacing shows no obvious change, organic content increases and the onset decomposition temperture decreases as the amount of benzoxazine hydrochloride added increases. Compared with pure BZ monomer, the onset ring-opening polymerization temperature of the mixture of BZ monomer and Bz-MMT decreases obviously. Compared with PBZ, the char yeild, tensile strength and impact strength of PBZ/Bz-MMT nanocomposites all are increased.