Poly(3-(p-methyl)benzyl-3,4-dihydro-6-methyl-2H-1,3-benzoxazine) (poly(pCpT)), which was obtained from electrochemical polymerization in acetonitrile/alkali aqueous solution, was characterized by FT-IR, UV-Vis and 1H-NMR. The results indicate a ring-opening structure of the polymer. By using a rotating-ring disc electrode (RRDE), the electrochemical behaviors of polymerization were studied and the polymerization mechanism was proposed.