Bioethanol

as a clean and renewable fuel

has gained increasing attention due to its major environmental benefits. Pervaporation (PV) is a promising and competitive technique for the recovery of ethanol from bioethanol fermentation systems due to the advantages of environmental friendliness

low energy consumption and easy coupling with fermentation process. The main challenge for the industrial application of ethanol perm-selective membranes is to break the trade-off effect between permeability and selectivity. As membrane is the heart of the pervaporation separation process

this article attempts to provide a comprehensive survey on the breakthroughs of ethanol perm-selective PV membranes from the perspectives of tailoring membrane materials to enhance PV separation performance. The research and development of polymeric and organic/inorganic hybrid membranes are reviewed to explore the fundamental structure–property-performance relationships. It is found that mixed matrix membranes with well-designed membrane structures offer the hope of better control overphysi-/chemical micro-environment and cavity/pore size as well as size distribution

which may provide both high permeability and membrane selectivity to break the trade-off effect. The tentative perspective on the possible future directions of ethanol perm-selective membranes is also briefly discussed

which may provide some insights in developing a new generation of high-performance PV membranes for ethanol recovery.