1,4:3,6-Dianhydro-α-d-glucopyranose (DGP) is one of important biomass pyrolysis anhydro sugar products that derive from the cellulose and hemicellulose components. There is no reliable method for the preparation of DGP at present, which contributed to its high cost with limited market supply and restricted applied research. In this study, we provided a novel method for the synthesis of DGP from methyl 3,6-anhydro-α-d-glucopyranoside for the first time. A mild and environmentally friendly synthetic approach for 3,6-anhydro glucopyranoside was developed