Ethanol, a versatile chemical extensively employed in several fields, including fuel production, food and beverage, pharmaceutical and healthcare industries, and chemical manufacturing, continues to witness expanding applications. Consequently, there is an ongoing need for cost-effective and environmentally friendly purification technologies for this organic compound in both diluted (ethanol-water–) and concentrated solutions (water-ethanol–). Pervaporation (PV), as a membrane technology, has emerged as a promising solution offering significant reductions in energy and resource consumption during the production of high-purity components. This review aims to provide a panorama of the recent advancements in materials adapted into PV membranes, encompassing polymeric membranes (and possible blending), inorganic membranes, mixed-matrix membranes, and emerging two-dimensional-material membranes. Among these membrane materials, we discuss the ones providing the most relevant performance in separating ethanol from the liquid systems of water–ethanol and ethanol–water, among others. Furthermore, this review identifies the challenges and future opportunities in material design and fabrication techniques, and the establishment of structure–performance relationships. These endeavors aim to propel the development of next-generation pervaporation membranes with an enhanced separation efficiency.