Anti-corrosive coatings for steel structures with an alternative anti-corrosive pigment, polyaniline was prepared and anti-corrosive characteristics of the prepared coatings were investigated. The structure of the polyaniline was identified by using FT-IR, UV/Vis. and TGA analysis, and the anti-corrosive properties were analyzed from the results of the salt spray experiment. We found that the anti-corrosion properties of the prepared coatings varied in accordance with the types of primer coating resins as well as with the existence and nonexistence of the top coating. In this condition, the properties of adhesion, chemical resistance, and water resistance were found to be very satisfactory when using the single-packaged urethane resin as the primer coating resin and the urethane resin as the top coating resin.