Electrochemical copolymerization of phenol and aniline was achieved on 304 stainless steel anodes in neutral water solution with an electrolyte of Na2SO4O4. Compared with pit corrosion potential of different copolymer coatings, the best solution composition was 0.09 mol/L phenol and 0.01 mol/L aniline. Through infrared spectrum analysis, polyaniline structure was proved in phenol-aniline copolymer, as well as more side chains. Scanning electron microscope was used to analyze microstructure of copolymer coating, taking advantage of part solubility of phenol-aniline eopolymer in tetrahydrofuran, the bifurcate network structure was observed. The copolymer coating microstructure was summarized, compared with the performance of polyphenol coatings, the reasons of corrosion resistance enhancement with the addition of aniline in electropolymerization reaction was assumed as well.