In　order　to　assemble　the　high　performance　pervaporation　complex　membrane,　the　pervaporation　complex　membranes　were　assembled　by　electrostatic　layer-by-layer　absorption　of　PEI/PAA　polyelectrolyte　on　hydrolyzed　polyacrylonitrile　(PAN)　ultrafiltration　support　membranes.　The　effects　of　hydrolysis　conditions　of　support　membranes　on　pervaporation　performance　of　complex　membranes　were　investigated.　The　appropriate　conditions　for　hydrolysis　were　when　time　is　60　min,　NaOH　concentration　is　2　mol/L　and　temperature　is　65°C.　In　addition,　the　assembly　process　of　polyelectrolyte　membranes　was　optimized.　The　unprotoned　hydrolysis　PAN　membranes　were　selected　as　the　support　membranes　while　ethanol　was　used　as　solvent　of　PEI　respectively.　Meanwhile,　the　effects　of　operation　conditions　on　the　pervaporation　separation　of　different　alcohol/water　mixtures　were　subsequently　researched.　It　was　found　that　the　larger　molecular　weight　of　alcohol,　the　better　the　pervaporation　performance　of　complex　membranes　is.　In　the　case　of　pervaporation　of　95%　t-butanol/water　mixtures,　under　the　temperature　of　70°C,　the　water　quality　ratio　in　the　permeate　and　the　permeate　flux　of　the　polyelectrolyte　complex　membranes　were　about　98.26%　and　346　g/(m2·h)　respectively.