Electrospun nanofiber membranes having a hierarchical structure with multilevel roughness were generated via electrospinning of poly(vinylidene fluoride) (PVDF)-SiO2 blend solutions. The composite PVDF-SiO2 nanofiber membranes were then endowed with superhydrophobicity by the fluorosilanization of the surface with low surface energy fluoroalkylsilane (FAS). The results showed that when the SiO2 content in the dope solutions increased from 0 wt% to 8 wt%, the water contact angles of the FAS modified nanofiber membranes increased significantly from 130.4 degrees to 160.5 degrees. The increment of the silica content in the dope solutions decreased the fiber diameters and pore sizes of the modified membranes, while the mechanical properties were enhanced with the silica addition. The liquid entry pressures of the membranes increased gradually from 84 kPa to 195 kPa with silica addition due to the increased contact angles and decreased pore size. Vacuum membrane distillation experiments were carried out for the modified nanofiber membranes to evaluate the anti-wetting properties. The optimal superhydrophobic nanofiber membrane maintained a stable flux of 31.5 kg m(-2) h(-1) with a permeate conductivity approximately 10 mu s cm(-1) over the entire test, while the fluxes and conductivities of the nanofiber membranes without superhydrophobicity showed a significant decrease and increase, respectively. The results indicated that the superhydrophobic modification process rendered the nanofiber membrane anti-wetting properties without compromising its excellent permeability.