The present investigation revealed how the surface morphology and hydrophobicity of polyvinylidene fluoride (PVDF) membranes, which were prepared via a vapor-induced phase separation (VIPS) method, were affected by the exposure time. The mass variation of the cast film was recorded. Membrane morphologies were observed by scanning electron microscopy (SEM) and thermal behaviors of membranes were examined by differential scanning calorimetry (DSC). Wide angle X-ray diffraction (WAXD) was employed to analyze the crystalline structures of the overall membranes and the surface layers. The results showed that different membrane morphologies and hydrophobicities could be obtained by changing the exposure time. A long exposure time facilitated the crystallization process, resulting in the formation of a porous skin and particle morphology, which increased the hydrophobicity of the surface. A short exposure time favored the formation of a digitate macrovoid and dense skin resulting from liquid-liquid phase separation in the immersion process, which reduced surface hydrophobicity. The water permeate flux in vacuum membrane distillation was greatly affected by the membrane porosity and surface hydrophobicity. (C) 2012 Elsevier B.V. All rights reserved.