This work demonstrates for the first time in open literature the dehydration by pervaporation of reactive mixtures encountered in the synthesis of ethyl acrylate. These mixtures contained, together with water and ethanol, highly reactive monomers, i.e., acrylic acid and ethyl acrylate. Among commercially available membranes, the Pervap#1201 of Sulzer Chemtech and the Zeolite-T of Mitsui were identified as promising membranes. As Pervap#1201 clearly performed better, it was selected for detailed pervaporation investigations. The total permeation flux of Pervap#1201 varied from 0.05 to 1.2 kg m(-2) h(-1) and the water permeance varied from 360 to 1700 GPU depending on the mass fraction of water in the feed (0.02-0.15) and the operating temperature (65-95 degrees C). Its separation factor (beta) toward water was greater than 4000 and the selectivity (alpha) was greater than 200. Permeate is essentially composed of water (0.99 mass fraction), ethanol (<0.007), acrylic acid (0.002) and ethyl acrylate (0.001). The permeate fluxes were modeled using the solution-diffusion approach and the estimated values showed good agreement with experimental values. The chemical stability of the Pervap#1201 membrane was investigated using continuous pervaporation experiments. Importantly, the performance of Pervap#1201 was demonstrated to be very stable, even after six months of immersion in a reaction mixture. Considering the pervaporation performances and the membrane stability in the presence of acrylic derivatives, the use of the Pervap#1201 membrane in the coupling reaction-esterification of ethyl acrylate appears to be very promising for industrial application. (C) 2013 Elsevier B.V. All rights reserved.