Poly(vinylidene fluoride) (PVDF) nanofiber membranes with different surface structures were obtained by controlling operating parameters in the electrospinning process. The diameters and assembling morphology of the PVDF nanofibers were characterized by scanning electron microscopy, nitrogen adsorption based on the BET (Brunauer, Emmett, and Teller) principle was applied to measure the specific surface area of the nanofiber membranes, the contact angles on the nanomembrane were evaluated by static micro-drop observation, and a modified Yang equation was applied to analyze the contact angles. The results revealed that the BET specific surface area was the key factor affecting the contact angles.