An integrated green process for the valorization of corn stover promoted by NaCl in GVL/H2O was developed. With the addition of NaCl in 25% GVL/H2O at 170 °C for 2 h, the interactions of NaCl (Na+ and Cl-) with -OH group in hemicellulose and G units in lignin were enhanced, which facilitated a high extraction of hemicellulose (96.4 wt%) and lignin (86.6 wt%), obtaining cellulose-rich solid residues. NaCl promoted the extracted hemicellulose degradation to produce small molecular products (85.6%). NaCl also promoted the cleavage of β-O-4′ linkages and decarboxylation reaction in lignin to obtain lower Mw (438 Da) oligomers and monophenols (14.2%) with high selectivity of 81.9% to 4-vinylphenol, 4-vinyl guaiacol and isoeugenol. Due to the salt effects of NaCl, the generated liquid products derived from hemicellulose and lignin were in situ separated by respectively dissolving into the aqueous and the GVL phase, which provided a possibility for further utilization. Additionally, the obtained cellulose-rich solid residues were activated by steam to prepare high performance activated carbon (SBET=819 m2/g, AMethylene blue=212 mg/g and AIodine=914mg/g), which showed great potential for pollution control within many industrial processes. This opened an avenue to integrate the valorization of corn stover.