Considering the urgent need for alternative biorefinery schemes based on sustainable development, this review aims to summarize the state-of-the-art in the use of deep eutectic solvent pretreatment to fractionate lignocellulose, with a focus on lignin recovery. For that, the key parameters influencing the process are discussed, as well as various strategies to enhance this pretreatment efficiency are explored. Moreover, this review describes the challenges and opportunities associated with the valorization of extraction-derived streams and highlights recent advancements in solvent recovery techniques. Furthermore, the utilization of computational models for process design and optimization is introduced, as the initial attempts at the economic and environmental assessment of this lignocellulosic bioprocess based on deep eutectic solvents. Overall, this review offers a comprehensive perspective on the recent advances in this emerging field and serves as a foundation for further research on the potential integration of deep eutectic pretreatment in sustainable multi-product biorefinery schemes.