Production of biofuels from renewable feedstocks has captured considerable scientific attention since they could be used to supply energy and alternative fuels. Bioethanol is one of the most interesting biofuels due to its positive impact on the environment. Currently, it is mostly produced from sugar- and starch-containing raw materials. However, various available types of lignocellulosic biomass such as agricultural and forestry residues, and herbaceous energy crops could serve as feedstocks for the production of bioethanol, energy, heat and value-added chemicals. Lignocellulose is a complex mixture of carbohydrates that needs an efficient pretreatment to make accessible pathways to enzymes for the production of fermentable sugars, which after hydrolysis are fermented into ethanol. Despite technical and economic difficulties, renewable lignocellulosic raw materials represent low-cost feedstocks that do not compete with the food and feed chain, thereby stimulating the sustainability. Different bioprocess operational modes were developed for bioethanol production from renewable raw materials. Furthermore, alternative bioethanol separation and purification processes have also been intensively developed. This paper deals with recent trends in the bioethanol production as a fuel from different renewable raw materials as well as with its separation and purification processes.