Publisher Summary The electrochemical behaviors of polymerization are explored by means of a rotating ring-disk electrode. There are two kinds of cations in different oxidation steps, which cause the chain propagation. Considering all the evidence, it is speculated that the electrochemically active species generated at lower potential undergo further oxidation at higher potential and result in polymer formation. The electrochemical synthesis of polymers is a well-established technique. A number of techniques for laboratory-scale synthesis of conducting polymers (such as polypyrrole, polythiophene, and polyanaline) are employed, of which the most important are the potentiostatic and galvanostatic methods. In the potentiostatic method, a predetermined optimum voltage is applied during synthesis, whereas in the latter, a fixed oxidation current is applied with no control over the resulting potential of the system. Electrochemical polymerization is rather suitable for metal protection. Actually in industry, protection against metal corrosion is often advantageously achieved by the electrodeposition of polymers such as polyphenols. Considering the reactivity of the benzoxazine rings and the convenient character of the electrochemical polymerization on conducting substrates, electrochemical polymerization of the benzoxazines appears to be a versatile method for preparing adherent polybenzoxazine coatings in the cases where metal protection is required. However, compared with the well- developed studies of the thermally activated polymerization of benzoxazines, only a few studies have focused on the electrochemical polymerization of benzoxazines. Unlike conducting polymers, the polybenzoxazines obtained are always insulators, which makes the electrochemical polymerization process on working electrodes rather difficult. Therefore, it remains a challenge to obtain a polybenzoxazine film on conductive substrates by electrochemical polymerization.