Abstract: In order to assemble the high performance pervaporation complex membrane,in this paper,the pervaporation complex membranes were assembled by electrostatic layer-by-layer absorption of PEI/PAA poly- electrolyte on hydrolyzed PAN ultrafiltration support membranes.The effects of hydrolysis conditions of sup- port membranes on pervaporation performances of complex membranes were investigated.The appropriate conditions for hydrolysis were when time is 60 mins,NaOH concentration is 2 mol/L and temperature is 65℃.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 alco- hol/water mixtures were subsequently researched.It was found that the larger molecular weight of alcohol, the better the performance of pervaporation of complex membranes is.In the case of pervaporation of 95% t- butanol/water mixtures,under the temperature of 70℃,the water quality ratio in the permeate and the per- meate flux of the polyelectrolyte complex membranes were about 98.26 % and 346 g/(m²·h),respectively.