In this work, hydrophobic polyaniline (PANI)/modified SiO2 composite coatings were prepared by drop-casting modified silica onto electrospun PANI coatings. The PANI/modified SiO2 composite coatings showed excellent corrosion protection properties. The superior protection property of the PANI/modified SiO2 coatings could be ascribed to the synergistic effect of three factors as follows: the electrochemical activity of PANI, the efficient filling of modified SiO2 nanoparticles into the voids of the electrospun PANI coating, and the high hydrophobicity of the hybrid PANI/modified SiO2 coatings. Specifically, the results indicate that PANI/modified SiO2 by the dodecyltrimethoxysilane (PANI/SiO2-DTMS) (CA = 95 degrees) coating has a self-repairing function and shows an anticorrosion efficiency of 99.99% for Q235 carbon steel, which was maintained at 99.99% after 71 days of immersion in 0.1 M H2SO4.