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The supercritical carbon dioxide extraction of bio-crude, produced by hydrothermal liquefaction of lignocellulosic biomass, was investigated for pressures and temperatures in the range 112–400 bar and 40–120 °C, corresponding to solvent densities in the range 548–882 kg/m 3. Total extraction yields ranged from 17 to 42%. For a given solvent density, temperature increase drastically improved both the process operability and efficiency. The extracts showed reduced density as well as 40% reduction of total acid number compared to the feed. The residue resulted to be partially deoxygenated. Ketones, 1-ring phenols and low molecular weight fatty acids were concentrated in the extract, with recoveries up to 80%, with ketones and phenols exhibiting the highest distribution factors. Observed selectivities suggest the feasibility of downstream separation of the key classes of extractives using supercritical carbon dioxide as a solvent.