AbstractBio-oil obtained from hydrothermal liquefaction of Salix psammophila is a very complicated mixture with some highly valued chemicals. In order to separate the chemicals from bio-oil, solvent extraction using nine solvents with different polarities were investigated in detail. The bio-oil extraction yield of the nine solvents were from high to low: tetrahydrofuran > toluene > ethyl acetate > acetone > ether > methylene chloride > methanol > petroleum ether > n-hexane. Based on their extraction yield, an efficient solvent combination of n-hexane, ethyl acetate, and tetrahydrofuran was used to separate the bio-oil through multistep extraction into three parts: light oil (26.13%), mid-weight oil (54.19%), and heavy oil (19.68%). These fractions were characterized by gas chromatography-mass spectrometry, Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance spectroscopy, and thermogravimetric analysis. The results showed that most of the highly valued chemicals were contained in the light oil; the mid-weight oil consisted of aromatic oligomer derived from the decomposition of lignin, which could be a promising candidate for partial substitute for petroleum-asphalt binder; the heavy oil was rich in alkanes.