Water, biomass, wind, and geothermal heat have the potential application as a viable substitute for traditional fossil fuels. Alternative renewable energy sources have been drawing more and more attention throughout the world in terms of environmental friendliness and economic viability. Over consumption of fossil fuels leads to the deterioration of the ecological environment, such as acid rain, and global warming. However, more than three-fourths of the worldwide consumed energy in 2040 is still supplied by non-renewable fossil energy sources (coal, natural gas, crude oil/petroleum, etc.). Nuclear energy consumption grows by 1% per year. Renewable energy is the world’s fastest growing form of energy source, and its consumption increases by 3% per year between 20. In the International Energy Outlook 20 (IEO2016 and IEO2019) Reference cases, total world energy consumption rises from 549 quadrillion British thermal units (Btu) in 2012 to 911 quadrillion Btu in 2050, an increase of nearly 66%. Finally, it is expected that more and more successful research could be realized into commercial products and this separation process will be deployed in industrial practices in the near future. Based on the facilitated transport mechanism, further exploration of ethanol-selective membranes may focus on constructing a well-designed microstructure, providing active sites for facilitating the fast transport of ethanol molecules, hence achieving both high selectivity and permeability simultaneously. Collectively, the quest is to break the trade-off between membrane permeability and selectivity. Overall, exploring the possibility and limitation of the separation performance of PV membranes for ethanol extraction is a long-standing topic. The recovery performance of the existing pervaporation membranes for ethanol solutions is compared, and the approaches to further improve the pervaporation performance are also discussed. The research and development of polymeric, inorganic, and mixed matrix membranes are reviewed from the perspective of membrane materials as well as modification methods. This overview of ethanol separation via pervaporation primarily concentrates on transport mechanisms, fabrication methods, and membrane materials. Pervaporation has achieved increasing attention because of its potential to be a useful way to separate ethanol from the biomass fermentation process. Bioethanol as a renewable energy resource plays an important role in alleviating energy crisis and environmental protection.