Due to the unique micro/nanoscale rough surface structures and water-repellency, the superhydrophobic surfaces hold great potential of anti-corrosive protection. This study reported a facile and controllable electrospinning technology to fabricate polyvinylidenefluoride (PVDF)/stearic acid (SA) nanofibers onto metal substrates for long-time anti-corrosive protection. Moreover, the anti-corrosion performances of the superhydrophobic nanofibers coated metal substrates were characterized by the Tafel polarization curve and electrochemical impedance spectroscopy (EIS). In addition, the electrochemical corrosion test results demonstrated the superhydrophobic PVDF/SA nanofibrous coatings possessed superior anti-corrosion performances for long-term metal substrates preservation, even after being immersed in a 3.5 wt% NaCl aqueous solutions up to 30 days. Therefore, we deeply believe the superhydrophobic PVDF/SA nanofibrous coatings could present a superior application prospect in anti-corrosive protection.