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Membrane distillation (MD) is attractive for water reclamation due to the fact of its unique characteristics. However, membrane wetting becomes an obstacle to its further application. In this paper, a novel hydrophobic polyvinylidene fluoride/poly(vinyl pyrrolidone) (PVDF/PVP) membrane was fabricated by electrospinning and solvothermal treatment. The electrospun membranes prepared by electrospinning showed a multilevel interconnected nanofibrous structure. Then, a solvothermal treatment introduced the micro/nanostructure to the membrane with high roughness (Ra = 598 nm), thereby the water contact angle of the membrane increased to 158.3 ± 2.2°. Owing to the superior hydrophobicity, the membrane presented high resistance to wetting in both NaCl and SDS solutions. Compared to the pristine PVDF membrane, which showed wetting with a flux decline (120 min for 0.05 mM surfactant solution treatment), the prepared membrane showed outstanding stability over 600 min, even in 0.2 mM surfactant solutions. These results confirm a simple method for anti-wetting hydrophobic membrane preparation, which presented universal significance to direct contact membrane distillation (DCMD) for industrial application.