The growing demand for energy and materials in modern society pushes scientific research to finding new alternative sources to traditional fossil feedstocks. The exploitation of biomass promises to be among the viable alternatives with a lower environmental impact. Making biomass exploitation technologies applicable at an industrial level represents one of the main goals for our society. In this work, the most recent scientific studies concerning the enhancement of lignocellulosic biomasses through the use of deep eutectic solvent (DES) systems have been examined and reported. DESs have an excellent potential for the fractionation of lignocellulosic biomass: the high H-bond capacity and polarity allow the lignin to be deconvolved, making it easier to break down the lignocellulosic complex, producing a free crystallite of cellulose capable of being exploited and valorised. DESs offer valid alternatives of using the potential of lignin (producing aromatics), hemicellulose (achieving furfural) and cellulose (delivering freely degradable substrates through enzymatic transformation into glucose). In this review, the mechanism of DES in the fractionation of lignocellulosic biomass and the main possible uses for the valorisation of lignin, hemicellulose and cellulose were reported, with a critical discussion of the perspectives and limits for industrial application.