AbstractAiming at obtaining greater value from the complicated composition of the bio-oil aqueous phase, solvents of increasing polarity were employed to sequentially separate the bio-oil aqueous phase using column chromatography. This not only relieved the catalyst deactivation, but also made it possible to obtain fractions rich in different chemical families to produce high-grade liquid fuels and valuable chemicals. Gas chromatography was adopted as a monitoring technology, and 11 fractions rich in different chemical families were obtained. The phenolic compounds in the aqueous phase were primarily eluted using dichloromethane. The strong polar benzenediols were enriched gradually in a dichloromethane fraction, and a high catechol content of 62.81% was achieved with the subsequent combination of a pH control method. Ethyl acetate gave three fractions, and pyrolytic sugars were the predominant compounds, whose highest content reached 67.86% in the third fraction. Further separation of the sugar-rich fraction using column chromatography could remove the residual phenolic compounds and furans and acquire a sugar fraction suitable for fermentation.