AbstractBACKGROUNDMembranes are the core and the main limitation of pervaporation. For example, in certain cases (more often for organic–organic mixtures) a pure product is not attainable as a permeate of a single stage and a series of membrane stages spaced by a condenser is required, making the process economically unacceptable.RESULTSThis work discusses the use of an alternative approach by exploring the multi‐stage‐batch‐pervaporation (MSBP) unit operation. Here, the permeate obtained after each batch‐stage is recycled to the feed tank to increase the permeate product purity in a following stage. The separation of methanol–methyl acetate mixtures was chosen as a case study.Simulations demonstrate how a multi‐stage‐batch‐pervaporation unit is able to meet product purity requirements, by varying the stage‐termination condition and the number of stages, employing a single membrane‐module and a single condenser.Moreover, a new way to visualize pervaporation separation performance of different membranes is proposed to replace the pervaporation separation index (PSI) analysis.CONCLUSIONBeing very flexible, the multi‐stage‐batch‐pervaporation unit operation could be of benefit for all small batch productions, even when using medium‐low performance membranes. Parts of continuous productions could also be suitable for multi‐stage‐batch‐pervaporation systems. © 2015 Society of Chemical Industry