Self-assembly of polyelectrolyte multilayer membranes (PEMMs) by using dynamic layer-by-layer (LBL) adsorption technique was conducted in this study. The polyethyleneimine (PEI) and polyacrylic acid (PAA) were alternatively deposited on the hydrolyzed polyacrylonitrile (PAN) ultrafiltration membranes under a pressure of 0.1 MPa. The changes of membrane surfaces were observed by using atomic: force microscopy. It was found that the regularity of the PEMMs was enhanced after the dynamic LBL assembly. The pervaporation separation behavior of various alcohol/water mixtures with the alcohols being t-butanol, 2-propanol and ethanol are compared with a relatively wide range of feed temperature and concentration.