A new kind of polybenzoxazine, poly(3(p-methyl) benzyl-3,4-dihydro-6-methyl-2H-1,3-benzoxazine), has been synthesized by an electrochemical method in acetonitrile/alkali aqueous solution. The obtained film shows good heat resistance properties. The structure of the obtained film is characterized using Fourier Transform Infrared (FTIR) spectroscopy.