Abstract A polymeric membrane (PERVAP® 2201) was used to study permselectivity and flux of water from esterification mixtures at different temperatures (30°C–90°C) and compositions. The pervaporation flux of water from binary mixtures such as butyl acetate/H2O, butanol/H2O, and acetic acid/H2O was accurately predicted by using a solution‐diffusion model with concentration‐dependent diffusion coefficients. Furthermore, on the basis of a lower activation energy of diffusion and higher flux for water, we concluded that butyl acetate production can be enhanced significantly by inserting a reactor membrane (PERVAP® 2201)in the esterification process. This research study was funded by the Sasol Centre of Separation and Technology (SST), and South Africa National Research Foundation (NRF).