Superhydrophobic surface is an enabling technology in numerous emerging and practical applications such as self-cleaning, anticorrosion, antifouling, anti-icing coatings, and oil-water separation. Here, we report a facile air-assisted electrospray approach to achieve a superhydrophobic surface by systematically studying spray conditions and the chemistry of a coating precursor solution consisting of silicon dioxide nanoparticles, polyacrylonitrile, and N,N-dimethylformamide. The wettability behavior of the surface was analyzed with contact angle measurement and correlated with surface structures. The superhydrophobic coating exhibits remarkable water and oil repellent characteristics, as well as good robustness against abrasion and harsh chemical conditions. This air-assisted electrospray technique has shown great control over the coating process and properties and thus can be potentially used for various advanced industrial applications for self-cleaning and anticorrosion surfaces.