To improve the neutral DES (choline chloride/glycerol) pretreatment performance, three environmentally friendly heteropoly acids (phosphotungstic, phosphomolybdic and silicotungstic acids) were used as catalysts. Pretreatment with silicotungstic acid at 120 °C for 3 h resulted in 97.3% of enzymatic digestibility at an enzyme loading of 15FPU/g substrate, which was approximately eight times more than that of raw samples. More importantly, 80% of glucose yield was obtained within 12 h. Simultaneously, 81.8% of ethanol yield was achieved in the SSSF process. The efficient conversion was ascribed to the significant delignification (89.5%), which resulted in the exposure of more accessible specific surface area. This was attributed to that the proton (H+) from heteropoly acids could significantly contribute to the lignin degradation. Intriguingly, trace acetic acid (0.39 g/L) and HMF (0.21-0.95 g/L) in the pretreatment liquor were produced without any significant deleterious effects. These discoveries provide new insights for efficient biomass conversion under mild conditions.