This chapter provides a comprehensive overview of the most recent advancements in ethanol recovery following fermentation of sugars from first-generation (1G), intermediate-generation (1.5G), and second-generation (2G) biomass. As the world seeks alternatives to fossil fuels, ethanol stands out for its potential in reducing greenhouse gas emissions and promoting sustainable energy systems. The chapter explores conventional and emerging separation technologies such as azeotropic and extractive distillation, adsorption, pervaporation, hybrid systems, and membrane technologies. It highlights specific challenges and innovations associated with each feedstock type, analyzing economic and environmental implications across production generations. Future trends are also discussed, including the integration of ethanol recovery into biorefinery systems, the role of artificial intelligence, and the development of low-energy and eco-friendly technologies. These insights contribute to understanding how technological innovation can optimize ethanol production and make it a more viable and sustainable solution in the global energy transition.