Selective permeation, driven by ionic attraction, is one of the most important properties of polyelectrolyte membranes. In this study, selective permeation behaviors of different polyelectrolytes, poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS), poly(styrene sulfonic acid) (PSS), and poly(methacrylic acid) (PMA), were studied via solution-diffusion mechanism. Among these three polyelectrolytes, PSS membranes showed the highest permeabilities for both water and dimethyl methylphophonate vapors due to their high diffusion coefficients caused by the high flexibility of PSS chains. It was also found that the cross-linking of polymer chains increased membrane permeabilities by weakening the physical network formed by ionic attraction. However, the type and cross-linking of polyelectrolytes did not have significant effect on the membrane selectivities. Nonwoven fabric was employed to control the selective permeation of polyelectrolyte membranes. It was found that filling the nonwoven fabric with polyelectrolytes led to composite membranes with reduced permeabilities and increased selectivities. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123: 227-233, 2012