The present investigation reveals how the surface morphology and the hydrophobicity of polyvinylidene fluoride (PVDF) membranes, which were prepared via a vapor-induced phase separation method, were affected by the initial PVDF content in the casting solution and the air temperature. The surface morphology was characterized with scanning electron microscopy. A ternary phase diagram of PVDF/N, N-dimethylacetamide/water was constructed to explain the formation mechanism of the different morphologies. The results show that different membrane morphologies and hydrophobicities can be obtained by changing the processing conditions. Low air temperature and high PVDF contents facilitate the crystallization process, resulting in the formation of a porous skin and particle morphology, which increases the hydrophobicity of the surface. High air temperature and low PVDF contents are favorable for the formation of a net-like surface morphology via spinodal decomposition and lead to a superhydrophobic surface. Theoretical calculations were performed to testify that the net-like surface was more favorable for superhydrophobicity than the particle-based surface. (C) 2012 Elsevier B.V. All rights reserved.