Na3PO4-H2O-assisted 1-butanol pretreatment was established for changing the structure of poplar waste and improving its enzymatic efficiency. After poplar waste was pretreated at 180 °C for 60 min, 51.3 % of xylan and 52.5 % of lignin were eliminated. After the enzymatic saccharification of treated poplar waste, the yield of reducing sugars reached 75.3 %. A series of characterizations demonstrated that Na3PO4-H2O-assisted 1-butanol pretreatment altered the poplar composition with improved cellulose accessibility from 231.2 to 459.5 mg/g and reduced surface area of lignin from 384.2 to 255.3 m2/g. Molecular simulations, quantum chemical calculations and independent gradient model analysis were performed on the poplar model, and the 1-butanol-Na3PO4-H2O pretreatment resulted in the increase of electrostatic and van der Waals repulsion forces in lignin and xylan, explaining the efficient lignin and xylan removal. A comprehensive interpretation of mass balance and energy flow was applied to assess the entire pretreatment process. This eco-friendly 1-butanol-Na3PO4-H2O pretreatment effectively broken the encapsulation of cellulose by enzyme inhibitors and improve biomass pretreatment effect.