This　paper　is　concerned　with　the　self-assembly　of　polyelectrolyte　multilayer　membranes　(PEMMs)　by　using　dynamic　layer-by-layer　(LBL)　adsorption　technique　for　pervaporation　separation　of　water/alcohol　mixtures.　The　polyacrylonitrile　(PAN)　ultrafiltration　membrane　used　as　a　support　was　firstly　hydrolyzed　with　alkaline　solutions　followed　by　alternatively　depositing　polyethylenei　mine　(PEI)　and　polyacrylic　acid　(PAA)　under　a　pressure　of　0.1　MPa.　The　PEI-ethanol　solution　and　PEI-aqueous　solution　were　used　to　investigate　the　effects　of　solvents　on　the　assembly　process.　It　was　found　that　both　separation　factor　and　permeate　flux　were　improved　remarkably　by　replacing　PEI　aqueous　solution　with　PEI-ethanol　solution.　Because　only　a　few　composite　bilayers　were　needed　to　achieve　a　good　capability　in　the　dynamic　LBL　process,　the　hydrolysis　degrees　of　PAN　support　membrane　would　strongly　affect　the　pervaporation　membrane　performances.　It　was　also　noted　that　the　exposure　of　membranes　to　low　pH　after　hydrolysis　would　not　benefit　for　the　assembly.　Further　studies　were　conducted　to　investigate　the　effects　of　alkali　species　on　the　PAN　hydrolysis　and　pervaporation　performances　of　PEMMs.　The　contribution　of　alkali　species　on　the　pervaporation　performance　was　in　the　order　of　KOH　＞　NaOH　＞　LiOH.　Finally,　the　performances　of　PEI/PAA　multilayer　membranes　assembled　on　the　hydrolyzed　PAN　support　were　evaluated　with　a　relatively　wide　range　of　feed　temperature　and　concentration.　The　PEMMs　obtained　with　only　2.5　bilayers　had　a　separation　factor　of　604　and　a　permeate　flux　of　314　g/m(2)h　(70　degrees　C)　for　pervaporation　of　95　wt%　ethanol-water　mixture.　(c)　2007　Elsevier　B.V.　All　rights　reserved.