The booming demand for energy across the world, especially for petroleum-based fuels, has led to the search for a long-term solution as a perfect source of sustainable energy. Lignocellulosic biomass resolves this obstacle as it is a readily available, inexpensive, and renewable fuel source that fulfills the criteria of sustainability. Valorization of lignocellulosic biomass and its components into value-added products maximizes the energy output and promotes the approach of lignocellulosic biorefinery. However, disruption of the recalcitrant structure of lignocellulosic biomass (LCB) via pretreatment technologies is costly and power-/heat-consuming. Therefore, devising an effective pretreatment method is a challenge. Likewise, the thermochemical and biological lignocellulosic conversion poses problems of efficiency, operational costs, and energy consumption. The advent of integrated technologies would probably resolve this problem. However, it is yet to be explored how to make it applicable at a commercial scale. This article will concisely review basic concepts of lignocellulosic composition and the routes opted by them to produce bioenergy. Moreover, it will also discuss the pros and cons of the pretreatment and conversion methods of lignocellulosic biomass. This critical analysis will bring to light the solutions for efficient and cost-effective conversion of lignocellulosic biomass that would pave the way for the development of sustainable energy systems.