Duplex PS/Ni-Ba-B coatings were prepared via dip coating of polystyrene film on electroless Ni-Ba-B layer. An electroless Ni-Ba-B coating with thickness of 6 ± 0.1 μm was deposited on steel substrate and subsequently a PS layer was dip coated on Ni-Ba-B coating. Morphology, structure, roughness, water contact angle, and corrosion behavior of the coatings were examined. SEM images on the cross section of duplex PS/Ni-Ba-B coating showed that the coating is uniform with good adhesion. The duplex coatings were amorphous and a combining of amorphous and crystalline phases. AFM observations revealed that the roughness of the duplex coatings decreased by increasing the weight percentage of PS. The highest hydrophobicity of the duplex coatings was attributed to 20% PS/Ni-Ba-B deposit. Electrochemical techniques were used for analysis of corrosion property of the coatings in NaCl solution. Presence of PS layer on the Ni-Ba-B coating significantly increased the corrosion resistance.