The　separation　of　methyl　tertiary　butyl　ether　(MTBE)　from　aqueous　solution　by　pervaporation-based　membrane　technology　has　attracted　much　attention　recently.　The　present　work　proposed　a　novel　strategy　to　enhance　the　MTBE/water　separation　performance　of　porous　α-Al2O3　membranes.　ZnO　seeds　were　planted　on　the　surface　of　α-Al2O3　membranes　by　the　deposition　and　decomposition　of　zinc　acetate,　followed　by　growing　ZnO　nanorod　arrays　(ZNA)　on　the　seeded　α-Al2O3　membranes　by　hydrothermal　reaction　in　the　mixed　hydrated　zinc　nitrate　(HZN)　and　hexamethylenetetramine　(HMTA)　solution.　Finally,　the　membranes　were　hydrophobized　by　grafting　fluoroalkylsilane　(FAS)　onto　their　surface.　The　results　show　that　the　MTBE/water　separation　factor　has　been　dramatically　promoted　from　7.7　for　the　α-Al2O3　membranes　to　55.7　for　the　ZNA-covered　α-Al2O3　membranes.　The　promotion　may　be　attributed　to　the　nearly　vertically　aligned　ZnO　nanorod　arrays,　which　provide　much　surface　area　to　load　more　fluorocarbon　groups　that　are　amiable　to　MTBE　molecules　and　supply　a　superhydrophobic　surface.　The　MTBE　in　the　permeate　mixture　has　been　concentrated　to　as　high　as　72.9　wt%,　in　striking　contrast　to　4.6　wt%　in　the　feed　solution.　The　obtained　membranes　are　highly　stable　upon　long-term　operation.　©　2023　Elsevier　B.V.