Asymmetric reverse osmosis (RO) polyamide (PA) composite membrane may be modified by means of a solvent-processing technique into pervaporation (PV) membrane for separating organic aqueous solution. Formic acid, acetic acid, phosphoric acid, hydrochloric acid, phenol, and so forth, better solvents for PA, were selected as the modifying agents in this study. The effect of the modifying conditions (type and concentration of the modifying agent, processing time of membrane in liquid medium) on the sorption of modified membranes was investigated. After the PA composite membrane was treated with 8 wt % acetic acid for 1 h, the swelling rate for water (S-w) increased, whereas that for isopropanol (S-IPA) decreased, compared with that of the nonmodified membrane. The difference between S-w and S-IPA of the membrane treated with acetic acid was greater than that with other modifying agents. The separation factor and flux of the modified membrane were correspondingly maximal when it was used in a PV separating isopropanol aqueous solution. The contact of solvent molecules in liquid medium with polymer chains in the PA membrane and the intranodular chains in the PA membrane tending to diffuse by reptation toward the solvent molecules were the principal causes leading to a change of structure of asymmetric PA composite membrane. The mechanism of changing membrane structure by means of the solvent-processing technique may better interpret the modification of PA composite RO membrane. (C) 2004 Wiley Periodicals, Inc.