As the world strides for renewable energy solutions, the integration of pulp and paper industries into the bioethanol production landscape emerges as a promising avenue. The pursuit of sustainable and eco-friendly alternatives have led to a paradigm shift in the biofuel landscape, with focus on leveraging the vast potential of pulp and paper industries for bioethanol production. The chapter delves into the innovative approach of utilizing lignocellulosic biomass (LCB), the primary raw material in paper production, as feedstock for bioethanol generation. By exploring the conversion of LCB into simpler sugars, researchers aim to establish a dual-purpose system, yielding both high-value paper products and bioethanol. This chapter provides a comprehensive overview of the ongoing efforts, shedding light on the key developments and challenges face towards making lignocellulosic bioethanol into commercial viable reality. Emphasizing critical role of pretreatment process hydrolysis in the production process, the chapter underscore the significance of this enzymatic or chemical breakdown of LCB as a primary key step for biofuel generation. The exploration of various hydrolysis techniques and their implications on bioethanol yield forms, a central theme, offering insights into optimizing this pivotal stage for enhanced efficiency and economic viability.