In this paper, superhydrophobic polyaniline (PANI)/polystyrene (PS) micro/nanostructures were prepared by an electrospinning combining with drop-cast strategy for protecting carbon steel. The corrosion resistance ability and durance property of the resultant PANI/PS micro/nanostructures in 0.1 M H2SO4 were investigated and compared using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization technique. It is found out that effective anticorrosion performance can be provided by PANI/PS micro/nanostructures for carbon steel, and the corrosion protection efficiency (eta) increases along with the water repellency of the PANI/PS micro/nanostructures. The protection properties of PANI/PS micro/nanostructures increased along with their water repellency. The PANI-PFOA/PS micro/nanostructures has the water contact angle value as high as 153 degrees, demonstrating the most excellent anticorrosion properties with a promising anticorrosion efficiency of 99.48%.