With the depletion of petroleum resources, the development of biobased vinyl ester resins as an alternative to petroleum-derived vinyl ester resins inspires researchers. However, the development of biobased vinyl ester resins with good thermal-mechanical properties, flame retardancy, and smoke suppression is in its infancy. In this work, the biobased vinyl ester resin monomer (((oxybis(4,1-phenylene))bis(azaneylylidene))bis(methaneylylidene))bis(2-methoxy-4,1-phenylene)bis(2-methylacrylate) (OBBBMA) with a Schiff base structure was prepared from renewable vanillin via a two-step reaction. The monomer was cured with styrene to obtain biobased vinyl ester resin (OBBBMA system), and the OBBBMA system was compared with the petroleum-derived vinyl ester resin (VER901). The OBBBMA system possesses a T g as high as 185.3 °C, which is much higher than that of VER901 (127.1 °C). The char residues of the OBBBMA system are 14 times that of VER901 in N 2 . Compared to VER901, the peak of heat release rate, the peak of smoke production rate, total smoke production, and CO production of the OBBBMA system decreased by 51, 48.6, 49.7, and 55%, respectively. The OBBBMA system shows a high T g , good flame retardancy, and smoke suppression and exhibits great potential to replace the petroleum-derived vinyl ester resin in high-performance applications.