Novel superhydrophobic electrospun poly(vinylidene fluoride) (PVDF) membranes with controllable structure and tunable wettability have been achieved through incorporating ZnO nanoparticles and ammonia treatment for PVDF and/or post-chemical treatment on polymer membrane. The maximum WCA (171 +/- 1.5 degrees) of the electrospun membrane can be achieved under the condition of adding 8 wt.% ZnO. The controllable micro/nano-structures grown on the electrospun fibers can be regulated by the nano-ZnO loading. The tunable wettability from hydrophobic to superhydrophobic or from superoleophilic to superamphiphobic can be realized through modifying PVDF membranes with aqueous ammonia solution and incorporating 1H,1H,2H,2H-perfluorodecyltriethoxysilane. Moreover, these superhydrophobic membranes also demonstrated excellent durability, anti-fouling property and oil-water separation ability after dozens of cycles. These promising PVDF nanocomposite membranes with controllable structure and tunable wettability have the potential values in large-scale application of filtration, oil-water separation and antifouling. (C) 2015 Elsevier Ltd. All rights reserved.