Biofuels could be defined as the fuels of the future, although much work is still required before they will replace fossil fuels. In this review, lignocellulosic biomass based on straw and related crops and wastes is described concerning its lignin contents, structure, and properties, and an overview on the means of current and predictable delignification protocols is presented. The discussion is focused on herbaceous monocot materials and their available pretreatments (physical, chemical, and enzymatic), with special emphasis on fungal ligninolytic enzymes and the most recent findings and developments in their current application, issues, and perspectives.