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The conventional fractionation of lignocellulose into cellulose, hemicellulose, and lignin was generally carried out at high temperatures and under highly acidic conditions owing to the rigid matrix of lignocellulose and crystallinity of cellulose, causing the degradation of carbohydrates and condensation of lignin, thus hindering their value-added utilization. In this study, a stepwise fractionation method was proposed in which microwave-assisted fractionation of hemicellulose under mild conditions contributed to 81.9% of xylose yield; then, the cellulose part solid was rapidly dissolved in LiBr molten salt hydrate (LiBr-MSH) solution, followed by a filtration process to isolate lignin solid. It was found that the removal of hemicellulose provided more pores for the next dissolution of cellulose, and LiBr-MSH caused the cleavage of the hydrogen bonds of cellulose. Consequently, the cellulose part solid was rapidly dissolved in LiBr-MSH. The results showed that under the optimal fractionation conditions, 78.0% yield of glucan oligomers and 89.7% purity of noncondensed lignin were obtained from cellulose fractionation and filtration, respectively. A high β-O-4 bond content close to 87.3% of the theoretical maximum yield was detected in the obtained lignin, indicating that most β-O-4 bond structure of lignin was well preserved. Additionally, the isolated lignin can be selectively depolymerized into aromatic monomers with a high yield of 20.4%, which is 74.2% of the theoretical maximum yield. [ABSTRACT FROM AUTHOR]