Separation of emulsified oil/water mixtures is urgently desired and worldwide challenge. Herein, a facile electrospinning technology was utilized to prepare polyvinylidenefluoride (PVDF)/stearic acid (SA) nanofibrous membranes onto mesh substrates for efficient separation of emulsified water-in-oil mixtures. Furthermore, the as-prepared PVDF/SA nanofibrous membranes showed robust superhydrophobicity with water contact angle above 154 degrees even after immersion in oils and corrosive solutions. More importantly, the as-fabricated nanofibrous membranes could effectively separate tiny water droplets from both surfactant-stabilized and surfactant-free water-in-oil emulsions with separation efficiency larger than 99.9%. All of these characteristics would make the superhydrophobic PVDF/SA nanofibrous membranes a great promise of realizing oil recovery in real word.