AbstractDense membranes made by crosslinking of poly(vinyl alcohol) (PVA) with poly(acrylic acid) (PAA) were prepared and tested in pervaporation and differential permeation of water–alcohol mixtures. Instead of a decrease of permeation flux as generally observed with most crosslinking agents, an increase in the permeability was observed with PAA crosslinked membranes at low PAA contents. The permeation flux increases with PAA contents in the polymer with no selectivity reduction for membranes containing less than 15 wt. PAA. The membranes show good performances to water–2‐propanol and water–ethanol mixtures, i.e. high fluxes and high selectivities to pure water. The membranes were stable and highly permeable to water. The enhancement of the permeability of PVA can be explained by a reduced crystallinity and an improved diffusivity due to the presence
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