Efficient pretreatment methods are crucial for the generation of fermentable sugars from the renewable lignocellulose. In this study, gamma-valerolactone (GVL), a biomass-derived green solvent, was used to fractionate corn stover (CS). The impact of different additives on the enzymatic hydrolysis and pretreatment of CS within the GVL/water system was carefully investigated. The results demonstrate that the use of H2SO4-assisted GVL/H2O (80:20, w/w) pretreatment at mild conditions successfully facilitates the depolymerization of CS, thereby improving the cellulase accessibility. Furthermore, by increasing the GVL pretreatment temperature to 160 degrees C with 100 mM H2SO4 addition, the pretreated CS led to nearly 100 % of hydrolysis yield at 2 % (w/v) solid load. Finally, the thermogravimetric analysis (TGA) was performed to evaluate the thermal decomposition characteristics of untreated CS and enzymatic residues based on the H2SO4-assisted GVL/H2O pretreatment. The results indicate that the enzymatic residues had two depolymerization stages from 200 degrees C to 500 degrees C with a final residual mass of 22.73 %, which was higher than that of untreated CS (20.56 %). Overall, this study provides an efficient lignocellulose pretreatment for fermentable sugars production and valorization of enzymatic residues.