Value-added oxygenates, such as acetic acid (HAc), glycolaldehyde and acetol, are present in pyrolysis oil and its cuts in substantial amounts. This work describes the separation of these value-added oxygenates from artificial aqueous fractions of pyrolysis oil via liquid-liquid extraction. Three phosphonium ionic liquids (ILs), two imidazolium ILs and one benchmark organic mixture (40 wt% tri-n-octylamine in 1-octanol: TOA/1-octanol) were applied as solvents. Although suited as solvent for HAc and glycolaldehyde, the benchmark TOA/1-octanol showed a low acetol distribution coefficient (0.05), which makes it less suitable for use in an integrated oxygenates extraction process. Phosphonium ILs showed the highest affinities for HAc and glycolaldehyde, and reasonable affinity for acetol. However, none of these solvents could be applied to remove all oxygenates from the aqueous solution in a single extraction step, because of the difficulty of oxygenates evaporation from phosphonium ILs and the reactivity of glycolaldehyde with P666,14[N(CN)2] in the presence of HAc, as was confirmed by NMR. Based on the good affinity of the imidazolium ILs for acetol, a two-step extraction process was proposed where Hmim[B(CN)4] may be used to extract acetol and HAc in the first step and be regenerated by evaporation of the solutes, and P666,14[Phos] may be applied to extract glycolaldehyde in the second step and be regenerated by back-extraction with water.