A novel class of photopolymerizable benzoxazines has been developed. This class has been coined as methacryloyl-functional benzoxazines. It has been synthesized by the reaction of the new benzoxazine monomers: (3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazin-6-yl)methanol and methacryloyl chloride. The structure of the monomer has been confirmed by Fourier transform infrared spectroscopy (FTIR) and H-1 and C-13 nuclear magnetic resonance spectroscopy (NMR). Its photopolymerization has been successfully carried out with and without photoinitiator, while the thermally activated polymerization is compromised by low temperature degradation.