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Novel benzoxazine (BOZ)/bismaleimide (BMI)/2,2′-diallylbisphenol A (BA), with a multiphase structure, was successfully prepared under the catalysis of methyl p-toluenesulfonate (PTSM) through reaction-induced phase separation. The curing reaction of BOZ with BMI and ring-opening polymerization of BOZ under the catalysis of PTSM were studied by Fourier transform-infrared spectroscopy and differential scanning calorimetry analyses, respectively. Mechanical measurements, thermogravimetric analysis, and microanalyses were conducted to assess the toughness and morphology of the composite. The reaction between BOZ and 4,4′-bismaleimidodiphenyl methane (BDM) occurs at a relatively high temperature. The ring-opening reaction of BOZ starts at a low temperature of 100°C because of the catalysis of PTSM. The BOZ/BDM/BA system with an appropriate amount of BOZ significantly improves the impact strength and flexural strength compared with those of the BA/BDM resin. The BOZ/BDM/BA system with PTSM also features high impact strength and flexural strength. Scanning electron microscopy images and energy-dispersive spectroscopy results show that BOZ-rich phase is dispersed in BDM-rich phase in the BOZ/BDM/BA system with PTSM. Thermogravimetric data show that the BOZ/BDM/BA blend with a multiphase structure exhibits superior thermal resistance to those of the BOZ/BDM/BA and BA/BDM resins. The formation mechanism of the ternary system under the catalysis of PTSM is elucidated with Gibbs free energy theory.