For many years, fossil fuels constituted the world’s primary source of energy. However, concerns about climate change and resource depletion necessitate a shift to renewable energy sources. Lignocellulosic biomass, derived from plants containing cellulose, hemicellulose, and lignin, is a promising source of sustainable bioenergy production. Its consumption reduces waste accumulation and dependency on finite fossil fuels. However, the primary challenge is to efficiently convert these materials into bioethanol while mitigating environmental impacts. To accomplish this goal, scientists are investigating different approaches including advanced pretreatment techniques, enzymatic hydrolysis, and microbial fermentation. These approaches are designed to increase bioethanol yields and reduce production costs and waste generation, advancing a more sustainable and environmentally friendly methodology. Recently, advancements in applied chemistry under extreme and unconventional conditions have led the way for potential commercial solutions in the market. High hydrostatic pressure, microwave, and ultrasound technologies are emerging as promising sustainable green pretreatment options for lignocellulosic biomass utilization in large-scale biorefineries. As the world moves toward a more sustainable energy future, advancements in bioethanol production from lignocellulosic waste materials are critical to lowering greenhouse gas emissions and mitigating environmental impacts. This book chapter provides a comprehensive overview of initiatives aimed at improving the sustainable production of biofuel from lignocellulosic waste, emphasizing both the environmental and economic aspects of this renewable energy source.