Pervaporative separation of trace organics from aqueous solutions was studied using poly(dimethyl siloxane) (PDMS) membrane at compositions up to saturation concentration of organics. The organics compounds studied were allyl isothiocyanate (AITC), 1-butanol, 2-phenyl ethyl alcohol (PEA), benzyl alcohol, aniline, benzaldehyde, nitrobenzene, and carbon tetrachloride. Except for AITC, all other compounds were found to yield high permeation selectivity. Effects of various approaches of solubility parameter approach were found to be most satisfactory in predicting permeation selectivity in terms of sorption behavior in the solute-solvent-polymer ternary system.