Abstract The concept of green chemistry is promoted by more fields. Therefore, it is necessary for the preparation of organic film under the gentle polymerization condition. In this article, the traditional strong acid polymerization electrolyte is replaced by a citric acid‐disodium hydrogen phosphate buffer system (pH 5.6). On the one hand, it reduces the negative effects of strong acid, and on the other hand, it avoids the damage of the metal substrate during the polymerization process. In addition, with o‐phenylenediamine (oPD) as the monomer, poly(oPD) (PoPD) films were successfully prepared by cyclic voltammetry under this system. The effects of concentration, temperature, and immersion time were investigated in 3.5 NaCl solution. It is found that temperature has a negative effect on the corrosion resistance of the coating. But when the temperature rises to 333 K, the resistance of the PoPD film is still five times higher than that of bare steel. The immersion test showed that when the film was immersed for 21.5 h, the impedance of the PoPD film was an order of magnitude larger than that of the bare steel that was impregnated at the same time. This research can provide new ideas for organic film in daily industrial production.
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