The　use　of　self-assembled　monolayers　(SAMs)　has　recently　been　recognized　as　an　effective　way　to　tailor　the　surface　properties　of　films　used　in　various　applications.　However,　application　of　SAMs　in　the　preparation　of　separation　membranes　remains　unexplored.　In　the　present　study,　surface-modified　poly(dimethylsiloxane)　(PDMS)　membranes　were　prepared　using　SAMs　to　fabricate　a　membrane　for　use　in　pervaporation　separation　of　ethanol/water　mixtures.　A　cross-linked　PDMS/polysulfone　(PSf)　composite　membrane　was　transformed　by　introducing　hydroxyl　functionalities　on　the　PDMS　surface　through　a　UV/ozone　conversion　process.　(Tridecafluoroctyl)triethoxysilane　was　allowed　to　be　adsorbed　on　the　resulting　Si-OH　substrate　to　increase　the　hydrophobicity　of　the　membrane.　Results　from　Fourier　transform　infrared　spectroscopy,　scanning　electron　microscopy,　energy-dispersive　X-ray　spectrometry,　atomic　force　microscopy,　and　contact　angle　analyses　suggest　that　the　fluoroalkylsilane　monolayer　was　successfully　formed　on　the　modified　PDMS/PSf　membrane　treated　by　60　min　UV/ozone　exposure.　The　newly　SAM-modified　membrane　exhibited　a　separation　factor　of　13.1　and　a　permeate　flux　of　412.9　g/(m(2)　h),　which　are　higher　than　those　obtained　from　PDMS　membranes.