Methane production via anaerobic digestion is a steadily growing industry in Europe and all over the world. Biomethane reduces the demand for fossil fuels, since it can be used for the production of power and heat or converted to vehicle fuel. Anaerobic digestion is a renewable energy technology; however, it can also be considered as a low-cost environmental-friendly waste management process, since it reduces the emission of greenhouse gases (GHGs), while it stabilizes the wastes. Currently, mainly the organic fraction of household waste, food waste, sewage sludge, manure, and energy crops is used for biogas production; nevertheless, there are a wide range of other organic substrates which can be utilized for biogas production. Among the organic matters, lignocellulosic materials have a great potential. Great abundance worldwide and carbohydrate-rich contents make them an attractive feedstock for biofuel production. Currently, anaerobic digestion of energy crops is widespread; however, biogas production from lignocellulosic residuals and wastes is still under investigation. This chapter focuses on anaerobic digestion of lignocellulosic materials. It explains the anaerobic digestion process and the current technologies used for crops digestion. It also summarizes the biogas potential of different lignocellulosic materials and the latest research on pretreatments to improve the methane yield. Finally, this chapter compares anaerobic digestion of lignocellulosic materials with energy production from these kinds of materials through thermochemical processes.