Sustainable processing of lignocellulosic biomass is meaningful for comprehensive biomass conversion. Here, a ball milling (BM) assisted biomass-derived ethylene glycol (BEG) pretreatment is proposed to removes nearly 90 % of the lignin and increases cellulose accessibility by 3 times than raw biomass, facilitating subsequent enzymatic saccharification or catalytic conversion for 5-hydroxymethylfurfural (HMF), achieving yields of 92.9 % and 32.6 %. The synergistic effect of BM/BEG positively impacted delignification, followed by saccharification and HMF conversion. Introduction of biomass-derived solvent recovers the lignin with a well-preserved chemical structure, uniform molecular weight, short side chains, and high purity, making it highly suitable for downstream utilization. Density functional theory revealed hydrogen bonding and good miscibility between BEG and lignin units, suggesting reaction mechanisms and pathways. Molecular dynamics simulations showed that the solubilizing effect of BEG on lignin promoted cellulase-cellulose binding, thereby enhancing saccharification efficiency. The successful use of BEG solvents to maximize the biomass value is conducive to achieve closed-loop biorefinery approaches.