Superhydrophobic nanocomposite coatings for magnesium surfaces with remarkable corrosion resistance were fabricated by electrospinning in the presence of fluorosilane-functionalized silica (SiO2) nanoparticles. The effects of surface-modified silica (mod-SiO2) nanoparticles on the superhydrophobicity and corrosion resistance of polystyrene (PS)/mod-SiO2 fiber coatings were evaluated. The incorporation of the SiO2 nanoparticles endows PS fibers with rough surfaces exhibiting a water contact angle (WCA) of 165 degrees. The surface wettability, corrosion resistance, and their relation to the inorganic content in the PS fibers and the contact angle of the composite coatings were explored. Analysis of the corrosion results confirmed that the PS/mod-SiO2 coating protected the Mg surface from corrosion. In addition, PS fibers containing mod-SiO2 nanoparticles showed improved hydrophobicity, and excellent corrosion resistance was achieved with PS fibers containing 4 wt% SiO2 nanoparticles.