The preparation of very hydrophobic poly(vinylidene fluoride) (PVDF) membranes was explored by using two methods. The first one was the modified phase inversion method using a water/N,N-dimethylacetamide (DMAc) mixture instead of pure water as a soft precipitation bath. The second method was a precipitation-bath free method, that is, the PVDF/DMAc casting solution underwent gelation in the open air instead of being immersed into a precipitation bath. The morphology of the surface and cross section of the membranes was investigated by using scanning electron microscopy (SEM). It was found that the membranes exhibited certain micro- and nanoscale hierarchical roughness on the surface, which brought about an enhanced hydrophobicity of the membrane. The contact angle (CA) of the samples obtained by the second method was as high as 150 degrees with water. The conventional phase inversion method preparing PVDF porous membrane using pure water as precipitation bath usually results in an asymmetric membrane with a dense skin layer having a CA close to that of a smooth PVDF surface. The modified approach avoided the formation of a skin-layer and resulted in a porous and highly hydrophobic surface of PVDF. (c) 2005 Wiley Periodicals, Inc.