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.