A wide range of homogeneous elastomeric membranes has been prepared using dicumylperoxide as a general cross-linking agent. The membranes have been used for both equilibrium sorption measurements and steady-state pervaporation experiments to study solution–diffusion phenomena in the removal of volatile organic components from aqueous solutions. Pervaporation experiments have been performed under identical hydrodynamic conditions in order to fix the boundary layer mass transfer coefficient at a constant and known value. For comparison of the permeabilities of different pervaporation membrane materials, this is of utmost importance. A wide range of selectivity factors up to a value of 100,000 are obtained, whereas usually the permeabilities for the organic component are in the range of 10−10−10−9m2/s and 10−14−10−12m2/s for water. The permeation and sorption data obtained for the various elastomers have been related to the chemical and physical nature of the elastomers through the solubility parameter and the glass transition temperature, respectively. Both diffusional and sorption effects seem to be important, determining the water-transport behavior in the elastomeric membranes. The solubility of the organic component appears to be independent of this combined solubility parameter. Differences in the permeabilities of the organic component can primarily be ascribed to structural parameters in the membrane material, like degree of unsaturation and presence of steric side groups. © 1993 John Wiley & Sons, Inc.