Production of bioethanol is winning support from masses because it is a workable choice to solve the problems associated with the fluctuating prices of crude petroleum oil, climatic change, and reducing non-renewable fuel reserves. First-generation biofuels are produced directly from food crops. The biofuel (bioethanol, biodiesel) is ultimately derived from the starch, sugar, animal fats, and vegetable oil that these crops provide. It is important to note that the structure of the biofuel itself does not change between generations, but rather the source from which the fuel is derived changes. Corn, wheat, and sugar cane are the most commonly used first-generation bioethanol feed stocks. Lignocellulosic materials are used as a feed stock for the production of second-generation bioethanol. The major production steps are (1) delignification, (2) depolymerisation, and (3) fermentation. Agricultural residues are waste materials produced through the processing of agricultural crops. The main reason to use of these agricultural residues to produce bioethanol is to convert waste to value added products. The main challenges are the low yield of the cellulosic hydrolysis process due to the presence of lignin and hemicellulose with cellulose. Pretreatments of lignocellulosic materials to remove lignin and hemicellulose are the techniques used to enhance the hydrolysis. Present review article comprehensively discusses the different pretreatment methods of delignification for ethanol production. Published literature on pretreatments from 1982 to 2018 has been studied. Perspectives, gaps in studies, and recommendations are given to fully describe implementation of eight prominent pretreatments (milling, pyrolysis, organic solvents, steam explosion, hot water treatments, ozonolysis, enzymatic delignification, and genetic modification) for future research. The energy and environmental features of lignocellulosic materials are elaborated to show a sustainable aspect of second-generation biofuel. It was felt necessary to discuss the concept of bio refinery to make biofuel production financially more attractive as well because the future prospects of second-generation biofuel are promising.