In the alcohol permselective pervaporation process, the hydrophobicity of the membrane usually plays an important role. The microstructure of membrane surface has significant influence on its hydrophobicity. In this study, a MCM-41@ZIF-8/PDMS hybrid membrane with micro- and nanoscaled hierarchical structure was prepared. ZIF-8 nanocrystal in situ grew on the surface of microscaled MCM-41 to fabricate MCM-41@ZIF-8 hybrid particles. These hybrid particles were modified by hydrophobic silane coupling agent to become superhydrophobic, and dispersed in PDMS matrix to form a composite membrane. The hydrophobicity of MCM-41@ZIF-8/PDMS membrane improved because of its hierarchical structure. The alcohol affinity of the membrane was thus enhanced. Moreover, owing to the porosity of MCM-41 and ZIF-8 particles, the flux of the hybrid membrane was significantly improved. The prepared MCM-41@ZIF-8/PDMS hybrid membranes exhibited a relative high flux (2201 g/m(2) h) with a separation factor of 10.4 in the separation of 5.0 wt% ethanol/water mixtures. In addition, these membranes can also be used in separating n-butanol/water mixtures with excellent separation performance. Therefore, the membrane is expected to have potential application in alcohol permselective pervaporation. (C) 2015 Elsevier B.V. All rights reserved.